Dissertations / Theses on the topic 'Metatext'

Thesis (Ph.D.)--Tufts University, 2001.
Adviser: Judith Haber. Submitted to the Dept. of English. Includes bibliographical references (leaves 206-212). Access restricted to members of the Tufts University community. Also available via the World Wide Web;

My first exposure to Brecht and his theories was as a high school drama student. One of our year twelve assessment tasks was to write and perform our own Brechtian drama using three or more alienation techniques. I wrote a piece about Religion and Fundamentalism, an issue that I felt strongly about at the time. By carefully following my teacher’s instructions and adhering to the assessment criteria I received a VHA. I concluded from this experience that political theatre could be made by following a simple recipe and combining key ingredients. As my knowledge of theatre and my own creative practice developed I came to understand the great complexity of Brechtian theory and the extreme difficulty of creating effective political theatre, that is, theatre that changes the world. Brecht’s theories have been so thoroughly absorbed into contemporary theatre practice that we no longer identify the techniques of Epic Theatre as necessarily political, nor do we acknowledge its radical origins. I have not yet seen a professional production of a Brechtian play but I’ve absorbed on countless occasions the brilliant reinterpretations of Brecht’s theories within the work of contemporary dramatists. My approach to creating political drama is eclectic and irreverent and I’m prepared to beg borrow and steal from the cannon of political theatre and popular media to create a drama that works, a drama that is both entertaining and provocative. Hoods is an adaptation for young audiences of my original play Kingswood Kids (2001). The process of re-purposing Kingwood Kids to Hoods has been a long and complex one. The process has triggered an analysis of my own creative practice and theory, and demanded an in-depth engagement with the theories and practice of key political theatre makers, most notably Brecht and Boal and more contemporary theatre makers such as Churchill, Kane, and Zeal Theatre. The focus of my exegesis is an inquiry into how the dramatist can create a theatre of currency that challenges the dominant culture and provokes critical thinking and political engagement in young audiences. It will particularly examine Brecht’s theory of alienation and argue its continued relevance, exploring how Brechtian techniques can be applied and re-interpreted through an in-depth analysis of my two works for young people, Hoods and Children of the Black Skirt. For the purposes of this short exegesis I have narrowed the inquiry by focusing on four key areas: Transformation, Structure, Pretext, Metatext.

My first exposure to Brecht and his theories was as a high school drama student. One of our year twelve assessment tasks was to write and perform our own Brechtian drama using three or more alienation techniques. I wrote a piece about Religion and Fundamentalism, an issue that I felt strongly about at the time. By carefully following my teacher’s instructions and adhering to the assessment criteria I received a VHA. I concluded from this experience that political theatre could be made by following a simple recipe and combining key ingredients. As my knowledge of theatre and my own creative practice developed I came to understand the great complexity of Brechtian theory and the extreme difficulty of creating effective political theatre, that is, theatre that changes the world. Brecht’s theories have been so thoroughly absorbed into contemporary theatre practice that we no longer identify the techniques of Epic Theatre as necessarily political, nor do we acknowledge its radical origins. I have not yet seen a professional production of a Brechtian play but I’ve absorbed on countless occasions the brilliant reinterpretations of Brecht’s theories within the work of contemporary dramatists. My approach to creating political drama is eclectic and irreverent and I’m prepared to beg borrow and steal from the cannon of political theatre and popular media to create a drama that works, a drama that is both entertaining and provocative. Hoods is an adaptation for young audiences of my original play Kingswood Kids (2001). The process of re-purposing Kingwood Kids to Hoods has been a long and complex one. The process has triggered an analysis of my own creative practice and theory, and demanded an in-depth engagement with the theories and practice of key political theatre makers, most notably Brecht and Boal and more contemporary theatre makers such as Churchill, Kane, and Zeal Theatre. The focus of my exegesis is an inquiry into how the dramatist can create a theatre of currency that challenges the dominant culture and provokes critical thinking and political engagement in young audiences. It will particularly examine Brecht’s theory of alienation and argue its continued relevance, exploring how Brechtian techniques can be applied and re-interpreted through an in-depth analysis of my two works for young people, Hoods and Children of the Black Skirt. For the purposes of this short exegesis I have narrowed the inquiry by focusing on four key areas: Transformation, Structure, Pretext, Metatext.

Visando contribuir para o entendimento dos processos anatéticos em rochas metamórficas de composição semipelítica, este trabalho apresenta dados de campo e modelagem metamórfica, utilizados como ferramentas para a correlação entre biotita xisto e metatexito ricos em quartzo e plagioclásio, com granada, cianita, muscovita, rutilo e ilmenita, pertencentes à unidade Santo Antônio no Sistema de Nappes Andrelândia, sul de Minas Gerais. Com o levantamento de campo foi caracterizada a associação cianita + granada + biotita + plagioclásio + muscovita + rutilo + ilmenita + quartzo + leucossoma tonalítico em litotipos que variam de xisto homogêneo a metatexito protoestromático, com o estabelecimento do protobandamento favorecido pela geração e segregação limitada do leucossoma, que aumenta da base para o topo do pacote. A amostragem dos litotipos principais é feita a partir de três pedreiras, da base para o topo: IC01, em que predomina xisto com feições de fusão in situ subordinadas às porções granoblásticas e cristais idiomórficos de plagioclásio em veios de quartzo; IC03, dominada por xisto, na base, e metatexito no topo, com ampla distribuição de patches, bolsões e veios de leucossoma tonalítico in situ ou in source; e IC07, caracterizada pelo bandamento de porções de xisto e metatexito, em escalas de 1 cm a 1 m, com leucossoma in situ ou in source reforçando o bandamento composicional, ou também na forma de veios, patches e bolsões que podem truncar a foliação. Com a química de rocha total é evidente que não existem diferenças composicionais significativas entre xistos e metatexitos. A geração de pequenos volumes de leucossoma rico em Si e Na, compatível com as segregações tonalíticas observadas, e resíduo rico em Fe, Mg e K, associado às acumulações de biotita nas suas bordas, não mudou de forma significativa a composição das rochas. A similaridade entre os padrões de elementos terras-raras reconhecidos para os litotipos analisados indica que a anatexia não alcançou condições altas o suficiente para a dissolução e reprecipitação de fases ultraestáveis como monazita e zircão, hipótese sustentada também pela ausência de feldspato potássico no leucossoma. O cálculo de isopletas resulta em topologia semelhante para amostras de IC01 e IC03; o plagioclásio em amostras das três pedreiras apresenta intervalo composicional contínuo entre An15 e An48, com grãos progressivamente mais ricos em albita, partindo dos inclusos em granada, na matriz xistosa ou metatexítica, e no leucossoma. Esta progressão na quantidade de albita é também observada em cristais de IC01 para IC03 e IC07, respectivamente, sentido no qual, em contrapartida, diminuem as diferenças composicionais entre cristais de mesma amostra e diferentes sítios texturais. A variação composicional da muscovita mostra grupos com distintos teores de sódio, sugerindo trajetória metamórfica horária para o pacote metatexítico e a termobarometria otimizada aplicada a IC01 e IC03 resulta em temperaturas de 750 a 850 °C para o pico metamórfico da base para o topo da unidade, respectivamente, em condições de pressão elevada, maior que 8 kbar. Estas evidências caracterizam o metamorfismo invertido atuante na região e demonstram a importância o reconhecimento da anatexia para a interpretação petrogenética de rochas semipelíticas.
As a contribution to the understanding of partial melting processes in metamorphic rocks of semipelite composition, this work presents field data and metamorphic modeling. They were used as tools for the correlation between biotite schist and metatexites, which are rich in quartz and plagioclase, with garnet, kyanite, muscovite, rutile and ilmenite, both rocks are correlated to the St. Antônio unit, in the Andrelândia Nappe System, south of Minas Gerais, Brazil. From the rocks field descriptions, it was characterized as the main mineral assemblage kyanite + garnet + biotite + plagioclase + muscovite + rutile + ilmenite + quartz + leucosome with tonalite composition, in rock types ranging from the homogeneous schist to the proto-stromatic metatexite. The compositional banding was enhanced by the generation and limited segregation of leucosome, and its proportion is higher from structural bottom to top of unit. Samples of the main rock types were collected in three quarries, from bottom to top: IC01, schist with sparse in situ melting features that are limited to the granoblastic portions and idiomorphic plagioclase crystals in quartz veins; IC03, dominated by schist, at the base, and metatexite, on top, with wide distribution of patches, pockets and veins of leucosome with tonalite composition, in situ or in source; and IC07, characterized by the compositional banding, varying from schist to metatexite, in bands with thickness ranging from 1 cm up to 1 m, and either in situ or in source leucosome veins enhance the compositional banding, although some veins, patches and pockets truncate the main foliation. With the whole rock chemistry analyses it is evident there are no significant compositional differences between schist and metatexite. The generation of small volumes of silicate Na-rich liquid is compatible with tonalite leucosome, and residue rich in Fe, Mg and K, associated with accumulations of biotite at its edges, but has not changed significantly the bulk rock compositions. The similarity of the of rare earth elements patterns for both rock types indicates anatexis did not reach a high degree and dissolution and reprecipitation of ultra-stable phases, as monazite and zircon, did not happen, which is sustained by absence of potassium feldspar in leucosome. The pseudosection modeling and isopleths calculation result in similar topology for samples of IC01 and IC03. Plagioclase crystals of the three quarries present continuous compositional change, between An 15 and An 48, with progressively more albite-rich crystals starting from the ones that are enclosed in garnet, in schist, metatexite matrix, and leucosome. This increase in the amount of albite is also observed in crystals from IC01 to IC03 and IC07, respectively, direction which, in turn, decrease the compositional differences between crystals of the same sample and different textural sites. The compositional variation of muscovite allows separation in groups with different quantities of Na, suggesting a clockwork P-T path to the rock, and optimized thermobarometry applied to IC01 and IC03 results in temperatures of 750-850 ° C for the metamorphic peak from base to top of the unit, in high pressure conditions, higher than 8 kbar. This P-T variation, from bottom to top, characterizes an inverted metamorphism in the region and demonstrates the importance of the recognition of anatexis processes for petrogenetic interpretation of semipelite rocks.

Neste trabalho foi estudada a reação de metátese do 10-undecenoato de metila (ou undecilenato de metila) catalisada por um novo sistema. WCl6-PMHS (polimetilhidrosiloxano). A reação foi comparada com alguns sistemas catalíticos já descritos na literatura. WCl6-SnMe4 e WCl6-Ph2SiH2 . As vantagens desse novo sistema são de ordem prática. uma vez que o PMHS é um líquido não volátil e não tóxico. e de ordem econômica, pois o PMHS tem um custo bastante inferior ao dos dois outros cocatalisadores citados. Os produtos da reação foram caracterizados por espectroscopia de RMN, IV e massas, e a seletividade determinada como próxima a 100%. Por estudos de IV, obteve-se evidências da coordenação da olefina ao metal, indicando que a reação segue o mecanismo proposto na literatura. Através da análise dos produtos secundários. e por analogia com a literatura, uma rota para a iniciação foi proposta. Por estudos com outros silanos, foi constatado, conforme descrito na literatura, que esse tipo de composto necessita da presença da ligação Si-H para ser útil como cocatalisador.
In this work, metathesis of methyl-10-undecenoate catalised by a new system. WCl6-PMHS (polymethylhydrosiloxane) has been s tudied. The reaction has been compa red with that catalised by some others catalytic systems aIready described the literature, WCl6-SnMe 4 and WCl6-Ph2SiH2 . The advantages of this new system are of praticaI order, once PMHS is a non-volatile and non-toxic Iiquid and economical order, because PMHS is Iess expensive than the two others systems refered above. The reaction products have been characterized by NMR, IR and MS, and the seIectivity determined as near 100%. By IR studies, we have obtained evidences for the coordination of the olefin to the metal, indicating that the reaction follows the mechanism proposed in the literature. Through the analysis of the secondary products, and by analogy with the literature, a iniciation path has been proposed. By studies with others silanes, it has been stated, as described in the literature, that this type of compound needs the presence of the Si-H bond to be useful as a cocatalyst.

Metates are stone objects on which corn and other substancesa re ground with hand-held stones called manos. Metates and manos have formed part of the standard household equipment in the Americas ever since settled life began to develop there in the 2nd millennium B. C. In Lower Central America - and specifically within the area bounded by eastern Honduras in the north and the Panama Canal in the south - prehispanic peoples fashioned some of their metates in a highly individual manner, often with a display of sophisticated and complex imagery both in form and decoration. They were made in this distinctive way over a period of at least 1500 years prior to the arrival of the Spaniards. The aim of this study is to show that, in spite of their diversity, these metates represent an unmistakable cultural trait which is particular only to the isthmian region of Central America. It is proposed that, as such, the decorated metate can serve as a diagnostic marker for essentially Lower Central American cultural traditions in prehispanic times. In earlier studies, many of these elaborately carved objects from Honduras, Nicaragua, Costa Rica and Panama have been referred to variously as 'altars', 'thrones', 'ceremonial tables', and - sometimes - as 'metates'. In the course of research for the present study it was found that the majority show traces of wear from grinding and that they can therefore be classified as metates. This thesis brings together material from the entire Lower Central American culture area and presents a comprehensive corpus of decorated metates from reported sites together with specimens available in museums and private collections. Based on some 650 examples, a classification is proposed which hasbeen organized according to formal attributes and supplemented by a stylistic analysis of recurring motifs and decorative patterns. A chronological and geographical framework has been added with the help of known data on decorated metates recovered from controlled excavations.

L'éthylène représente l'une des molécules plateforme les plus importantes de l'industrie de la chimie avec une capacité de production de l'ordre de 140 millions de tonnes par an. La recherche réalisée dans cette thèse porte sur le développement de nouveaux catalyseurs hétérogènes, ainsi que des procédés pour l'oligomérisation et la métathèse de l'éthylène. Les catalyseurs sont des matériaux mésoporeux (topologie SBA-15 ou SiO2 commerciale) au Ni (pour l'oligomérisation) et au Mo (pour la métathèse). Les catalyseurs Ni-AlSBA-15 (~ 2,6% Ni, Si/Al ~ 7) ont été préparés par alumination post-synthèse de la silice SBA-15 avec de l'aluminate de sodium, suivie d'un échange d'ions avec du nickel. D'une manière similaire ont été préparés les catalyseurs Ni-AlSiO2. Les techniques de caractérisation, telles que diffraction des rayons X, sorption d'azote, MET, RMN de 27Al et 29Si ont prouvé le système de pores parfaite des solides SBA-15, avec de l'aluminium coordonnée principalement en mode tétraédrique dans le réseau de silice. Ni-AlSBA-15 et Ni-AlSiO2 présentent des comportements catalytiques exceptionnels dans la réaction d'oligomérisation de l'éthylène. A 150 ° C et 3,5 MPa, à la fois en mode discontinu et en flux, les catalyseurs sont très actifs (jusqu'à 175 g d'oligomères par gramme de catalyseur et par heure), sélectifs (oléfines en C4, C6, C8 et C10, aucun des produits de craquage) et stable (taux de conversion élevé pendant 80 h de réaction). Ces performances sont supérieures à celles présentées par d'autres catalyseurs hétérogènes à base de Ni, sans utiliser cocatalyseurs alkylaluminium. Un mécanisme impliquant des ntermédiaires metallocycliques est soutenu par nos résultats expérimentaux. Nous avons aussi développé un procédé original pour convertir directement l'éthylène en propylène, à travers des réactions en cascade, d'oligomérisation, d'isomérisation et de métathèse, avec deux catalyseurs hétérogènes solides très actifs. Dans un seul réacteur à flux et dans des conditions identiques, l'éthylène a été dimérisé/isomérisé sélectivement sur Ni-AlSBA-15 pour former le 2-butène, qui réagit avec l'excès d'éthylène dans une deuxième étape, sur un catalyseur au MoO3 pour produire du propylène. A 80 ° C et 3 MPa, des activités spécifiques allant jusqu'à 48 mmoles de propylene par gramme de catalyseur et par heure ont été obtenues. La désactivation et la régénération des catalyseurs ont été étudiées. Un mécanisme, en trois étapes (dimérisation/isomérisation/métahèse), sur trois sites différents (Ni+, H+ et respectivement Mo6+) a été proposé. MOTS CLES : éthylène ; propylène ; oligomérisation ; métathèse ; catalyse hétérogène ; Ni-AlSBA-15 ; MoO3
Ethylene is one of the most important platform molecules of the chemical industry with a production capacity of around 140 million tons per year. The research conducted in this thesis focuses on the development of new heterogeneous catalysts and processes for the oligomerization and metathesis of ethylene. The catalysts are mesoporous materials (SBA-15 topology or commercial SiO2) with Ni (for the oligomerization) and with Mo (for metathesis). Ni-AlSBA-15 oligomerization catalysts (2.6 wt% Ni, Si/Al = 7) were prepared by post-synthesis alumination of SBA-15 silica with sodium aluminate, followed by ion exchange with nickel. In a similar manner was prepared the catalyst Ni-AlSiO2. Characterization techniques, including powder X-ray diffraction, N2 sorption, TEM, 27Al and 29Si MAS NMR proved the perfect pore system of the SBA-15 materials, with aluminum tetrahedrally mainly coordinated in the silica framework. Ni-AlSBA-15 and Ni-AlSiO2 exhibited outstanding catalytic behaviour in the oligomerization reaction of ethylene. At 150 °C and 3.5 MPa, in both batch and flow mode, the catalyst was highly active (up to 175 g of oligomers per gram of catalyst per hour), selective (C4, C6, C8, and C10 olefins, no cracking products) and stable (high conversion during 80 h on-stream). These performances were superior than those exhibited by other Ni-based heterogeneous catalysts, without using alkylaluminum cocatalysts. A mechanistic pathway involving metallacyclic intermediates is supported by the experimental results. Additionally, an original process for converting ethylene to propylene, involving cascade oligomerization/isomerisation/metathesis reactions, over two robust and highly active heterogeneous catalysts has been proposed. In a single flow reactor and under identical conditions, ethylene was first selectively dimerized/isomérized over Ni-AlSBA-15 catalyst to form 2-butene, which reacted then with the excess of ethylene over MoO3–based catalyst, to produce propylene. At 80°C and 3 MPa, specific activities up to 48 mmol of propylene per gram of catalyst per hour were obtained.KEYWORDS : ethylene ; propylene ; oligomerization ; metathesis ; heterogeneous catalysis ; Ni-AlSBA-15; MoO3

Orientador: Regina Buffon
Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica
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Mestrado

O esgotamento de recursos fósseis aliado à poluição causada pelas fontes não renováveis clamam por novas rotas sustentáveis. Importante componente da biomassa são os óleos vegetais e esses possuem potencial para suprir a demanda não só de energia, mas também de produtos químicos e materiais. A isomerização e metátese de ésteres de óleos vegetais forma olefinas, ésteres e diésteres com diferentes comprimentos de cadeia carbônica e podem ser utilizados para produção de polímeros, dieseis, lubrificantes, detergentes, revestimentos de superfície, produtos farmacêuticos, cosméticos ou modificados para uma variedade enorme de outros compostos. Neste trabalho inicialmente foram estudadas reações em tandem de isomerização e metátese utilizando 1-octeno como substrato modelo. Dois sistemas foram utilizados para a captura de compostos voláteis em reações de isomerização/metátese. O sistema B de pressão atmosférica 1 atm (sistema aberto) apresentou melhor distribuição de produtos com cadeia longa e a maior captura de olefinas leves em comparação com o sistema A de pressão reduzida (sistema fechado). Estudou-se também o efeito da compatibilidade catalítica e a distribuição de produtos obtida pela combinação entre três catalisadores de metátese de olefinas Hoveyda Grubbs de primeira geração - HG1, Hoveyda Grubbs de segunda geração - HG2 e Umicore M42 - UM42 e dois catalisadores de isomerização de olefinas clorohidreto-carboniltris(trifenilfosfina)rutênio(II) - RuH e bromotriterc-butilfosfinapaladio-(I) - PdBr, no qual, a concomitância entre os catalisadores HG2 / RuH, UM42 / PdBr, HG2 / PdBr e HG2 / PdBr produziram espécies obedecendo uma distribuição em equilíbrio. Entretanto, quando foi utilizado HG1 / RuH não ocorreu formação do equilíbrio devido a aparente desativação do catalisador de isomerização RuH pela fosfina dissociada do catalisador HG1. Reações em tandem de isomerização/metátese a partir de ésteres de óleos de oliva e ésteres de óleo de girassol também foram investigadas. Três combinações entre catalisadores de isomerização e metátese, HG2 / RuH, UM42 / RuH e UM42 / PdBr, foram utilizadas e as combinações apresentaram diferentes distribuições de produtos olefínicos, ésteres e diésteres formados. Quando o substrato empregado foi o éster de óleo de oliva ocorreu a formação de três equilíbrios. Utilizando éster de óleo de girassol como substrato não ocorreu formação de equilíbrio devido a conjugação da dupla ligação. O catalisador de metátese de olefinas UM42 necessita ativação que é realizado pelos catalisadores de isomerização RuH e PdBr. Dois mecanismos foram propostos para explicar essas observações. A ativação do UM42 pelo RuH ou PdBr foi explicado pela formação de complexos B e C ou B e E, respectivamente. Foi sugerido que o complexo B com 14 elétrons seja ativo para metátese. Enquanto o complexo C e E podem formar espécies capazes de realizar isomerização de olefinas.
The depletion of fossil resources combined with pollution from non-renewable sources clamoring for new sustainable routes. Important component of biomass are vegetable oils that can supply not only the energy, but also chemicals and materials demand. The isomerization and metathesis of vegetable oils esters form olefins, esters and diesters with different carbon chain lengths and may be used for producing of polymers, diesel, oils, detergents, surface coatings, pharmaceuticals, cosmetics or modified for a wide variety of other compounds. In this work, initially tandem isomerization/metathesis reactions of 1-octene as a model substrate were studied. Two systems were used for the capture of volatile compounds in isomerization/metathesis reactions. The system B (open system) showed a better product distribution for high-molecular weight olefins and best system for the capture of low molecular weight (“light”) olefins in comparison with system A (reduced pressure). The catalyst compatibility and product distribution obtained by combining three olefin metathesis catalysts Hoveyda Grubbs 1st generation - HG1, Hoveyda Grubbs 2nd generation - HG2 and Umicore M42 - UM42 and two olefin isomerization catalysts bromotri-tert-butylphosphine-palladium(I)dimer - PdBr e chlorohydridocarbonyltris(triphenylphosphine)-ruthenium(II) - RuH, in which the catalyst combinations HG2 / RuH, UM42 / PdBr, HG2 / PdBr and HG2 / PdBr operating in a Tandem fashion resulted in a mixture of products exhibiting an equilibrium distribution. However, when the combination HG1 / RuH was used the equilibrium did not occur, likely due to deactivation of the RuH isomerization catalyst by the dissociated phosphine from the metathesis catalyst HG1. Tandem isomerization/metathesis reactions of transesterified olive and sunflower oils were investigated. Three combinations of catalysts HG2 / RuH, UM42 / RuH and UM42 / PdBr showed different products distributions of olefins, esters and diesters. The formation of three equilibrium distributions could be observed when transesterified olive oil was used as substrate. When the substrate was transesterified sunflower oil, no equilibrium mixture was obtained due to the formation of conjugated double bonds. The olefin metathesis catalyst UM42 requires activation, which occurred in the presence of both isomerization catalysts RuH and PdBr. Two mechanistic pathways have been proposed to explain these observations. The activation of UM42 by RuH or PdBr was explained through the formation of the complexes B and C or B and E, respectively. The 14 electron complex B is suggested to be metathesis active, while the complexes C and E may form species able to perform olefin isomerization.

Neste trabalho, realizou-se reações de metátese e isomerização em tandem, utilizando 1-octeno como substrato, com o objetivo de obter olefinas de baixo peso molecular. Além disso, estudou-se também a etenólise de óleo de oliva em baixas pressões de etileno (1-4 bar), visando a posterior utilização dos produtos obtidos, olefinas terminais, em reações de isomerização e metátese em tandem. Nas reações de isomerização e metátese em tandem de 1-octeno utilizou-se os catalisadores de Grubbs de segunda geração G-2, o catalisador de Hoveyda-Grubbs de segunda geração HG-2 e o catalisador de isomerização RuClH(CO)(PPh3)3 [RuH] em três sistemas diferentes e à diferentes temperaturas. Em todos os sistemas obteve-se uma distribuição de produtos com diferentes números de carbonos, indicando que, em todos os casos, as reações de isomerização e metátese ocorreram. No primeiro sistema, utilizou-se os catalisadores HG-2 e [RuH] à 50 e 100 °C, em um fluxo de argônio. Neste sistema, observou-se que com o aumento da temperatura, a concentração de todos os produtos diminuiu, indicando que o aumento da temperatura favorece a remoção dos produtos voláteis, deslocando a distribuição dos produtos para a formação destes. No segundo sistema, utilizou-se os catalisadores G-2 e [RuH] à 50, 100 e 150 °C, e a reação foi realizada em um reator Parr. Neste sistema, não se observou uma diminuição da concentração dos produtos com o aumento da temperatura. Os resultados obtidos neste sistema, indicam haver uma certa incompatibilidade entre os catalisadores utilizados. Entretanto, uma distribuição de produtos característica de reações de isomerização e metátese em tandem foi obtida, mostrando que ambas as reações ocorreram. Desta forma, verificou-se, em separado, se à 150 °C ambos os catalisadores permaneciam ativos. Os resultados obtidos mostraram nesta temperatura, somente o catalisador de metátese G-2 efetua as duas transformações. No terceiro sistema, utilizou-se os catalisadores G-2 sozinho ou os catalisadores HG- 2 e [RuH] para efetuar reações em tandem com a captura dos produtos voláteis formados, a 100 e 150 °C. Melhores resultados foram obtidos com os catalisadores HG-2 e [RuH] a 150 Por fim, estudou-se a etenólise de óleo de oliva em baixas pressões de etileno catalisada pelos catalisadores de Grubbs de primeira G-1 e segunda geração G-2, e catalisador de Hoveyda-Grubbs de segunda geração HG-2 em pressões de etileno de 1 a 4 bar, por períodos de 0,5 a 3 horas, a 50 °C. Conversões de até 70 %, calculadas por RMN-1H, foram obtidas. Dentre os catalisadores estudados, G-1 e G-2 resultaram em praticamente a mesma conversão, enquanto que HG-2 resultou em uma conversão significativamente menor. Em relação ao tempo reacional, obteve-se conversões de 50 % após 0,5 h de reação. O aumento do tempo de reação para 2,0 h resultou em um ligeiro aumento de conversão de 61 %. Estudou-se ainda a influência da utilização de óleo não purificado e de óleo de soja (purificado). Resultados significativemente inferiores em relação aqueles encontrados com óleo de oliva purificado foram obtidos.
In this work, tandem isomerization and metathesis reactions were performed using 1- octene as substrate in order to obtain low molecular weight olefins. In addition, the ethenolysis of olive oil at low ethylene pressures (1-4 bar) were also studied with the aim to use the products, terminal olefins, in tandem isomerization and metathesis reactions. In the 1-octene tandem isomerization and metathesis reactions the Grubbs G-2 and Hoveyda-Grubbs HG-2 second generation catalysts and isomerization catalyst RuClH(CO) (PPh3)3 [RuH] were used in three systems at different temperatures. In all systems, a product distribution with different carbon numbers were obtained, indicating that in all cases, both isomerization and metathesis reactions occurred. In the first system, the catalysts HG-2 and [RuH], at 50 and 100 °C were applied, under an argon flow. In this system, the higher temperature decreased the concentration of all products, indicating that the temperature increase favored the removal of volatile products and this shifted the product distribution to the formation of the volatile products. In the second system the catalysts G-2 and [RuH] were used at 50, 100 and 150 °C, and the reaction was performed in a Parr reactor. In this system, the concentration of products did not decrease with the increase of the temperature. The results obtained with this system indicated that there is some level of incompatibility between the catalysts used. However, a product distribution characteristic for tandem isomerization and metathesis reactions was obtained, showing that both reactions occurred. Besides that, both catalysts remained active when used idividually at 150 °C. Interestingly, only the metathesis catalyst G-2 can perform both transformation at 150 °C in the same way when the two catalysts G-2 and [RuH] are used. In the third system, only catalyst G-2 or both catalysts HG-2 and [RuH] were used to perform tandem reactions, together with the capture of volatile products formed at 100 and 150 °C. The best results were obtained with the catalysts HG-2 and [RuH] at 150 °C. Finally, the olive oil ethenolysis at low pressures of ethylene catalyzed by first G-1 and second G-2 generation Grubbs catalysts, and second generation Hoveyda-Grubbs catalyst HG-2 at ethylene pressures ranging from 1 to 4 bar was studied at 50 °C for períods of 0,5 to 3 hours. Conversions of up to 70 % determined by 1H-NMR, were obtained. Among the catalysts studied, G-1 and G-2 displayed almost the same conversion, whereas HG-2 displayed a significantly lower conversion. Regarding the reaction time, a conversion of 50% was obtained after 0.5 h. The increase of the reaction time to 2.0 h resulted in a slightly improved conversion of 61 %. Both umpurified olive oil and purified soybean oil resulted in significatively inferior conversions.

O esgotamento de recursos fósseis aliado à poluição causada pelas fontes não renováveis clamam por novas rotas sustentáveis. Importante componente da biomassa são os óleos vegetais e esses possuem potencial para suprir a demanda não só de energia, mas também de produtos químicos e materiais. A isomerização e metátese de ésteres de óleos vegetais forma olefinas, ésteres e diésteres com diferentes comprimentos de cadeia carbônica e podem ser utilizados para produção de polímeros, dieseis, lubrificantes, detergentes, revestimentos de superfície, produtos farmacêuticos, cosméticos ou modificados para uma variedade enorme de outros compostos. Neste trabalho inicialmente foram estudadas reações em tandem de isomerização e metátese utilizando 1-octeno como substrato modelo. Dois sistemas foram utilizados para a captura de compostos voláteis em reações de isomerização/metátese. O sistema B de pressão atmosférica 1 atm (sistema aberto) apresentou melhor distribuição de produtos com cadeia longa e a maior captura de olefinas leves em comparação com o sistema A de pressão reduzida (sistema fechado). Estudou-se também o efeito da compatibilidade catalítica e a distribuição de produtos obtida pela combinação entre três catalisadores de metátese de olefinas Hoveyda Grubbs de primeira geração - HG1, Hoveyda Grubbs de segunda geração - HG2 e Umicore M42 - UM42 e dois catalisadores de isomerização de olefinas clorohidreto-carboniltris(trifenilfosfina)rutênio(II) - RuH e bromotriterc-butilfosfinapaladio-(I) - PdBr, no qual, a concomitância entre os catalisadores HG2 / RuH, UM42 / PdBr, HG2 / PdBr e HG2 / PdBr produziram espécies obedecendo uma distribuição em equilíbrio. Entretanto, quando foi utilizado HG1 / RuH não ocorreu formação do equilíbrio devido a aparente desativação do catalisador de isomerização RuH pela fosfina dissociada do catalisador HG1. Reações em tandem de isomerização/metátese a partir de ésteres de óleos de oliva e ésteres de óleo de girassol também foram investigadas. Três combinações entre catalisadores de isomerização e metátese, HG2 / RuH, UM42 / RuH e UM42 / PdBr, foram utilizadas e as combinações apresentaram diferentes distribuições de produtos olefínicos, ésteres e diésteres formados. Quando o substrato empregado foi o éster de óleo de oliva ocorreu a formação de três equilíbrios. Utilizando éster de óleo de girassol como substrato não ocorreu formação de equilíbrio devido a conjugação da dupla ligação. O catalisador de metátese de olefinas UM42 necessita ativação que é realizado pelos catalisadores de isomerização RuH e PdBr. Dois mecanismos foram propostos para explicar essas observações. A ativação do UM42 pelo RuH ou PdBr foi explicado pela formação de complexos B e C ou B e E, respectivamente. Foi sugerido que o complexo B com 14 elétrons seja ativo para metátese. Enquanto o complexo C e E podem formar espécies capazes de realizar isomerização de olefinas.
The depletion of fossil resources combined with pollution from non-renewable sources clamoring for new sustainable routes. Important component of biomass are vegetable oils that can supply not only the energy, but also chemicals and materials demand. The isomerization and metathesis of vegetable oils esters form olefins, esters and diesters with different carbon chain lengths and may be used for producing of polymers, diesel, oils, detergents, surface coatings, pharmaceuticals, cosmetics or modified for a wide variety of other compounds. In this work, initially tandem isomerization/metathesis reactions of 1-octene as a model substrate were studied. Two systems were used for the capture of volatile compounds in isomerization/metathesis reactions. The system B (open system) showed a better product distribution for high-molecular weight olefins and best system for the capture of low molecular weight (“light”) olefins in comparison with system A (reduced pressure). The catalyst compatibility and product distribution obtained by combining three olefin metathesis catalysts Hoveyda Grubbs 1st generation - HG1, Hoveyda Grubbs 2nd generation - HG2 and Umicore M42 - UM42 and two olefin isomerization catalysts bromotri-tert-butylphosphine-palladium(I)dimer - PdBr e chlorohydridocarbonyltris(triphenylphosphine)-ruthenium(II) - RuH, in which the catalyst combinations HG2 / RuH, UM42 / PdBr, HG2 / PdBr and HG2 / PdBr operating in a Tandem fashion resulted in a mixture of products exhibiting an equilibrium distribution. However, when the combination HG1 / RuH was used the equilibrium did not occur, likely due to deactivation of the RuH isomerization catalyst by the dissociated phosphine from the metathesis catalyst HG1. Tandem isomerization/metathesis reactions of transesterified olive and sunflower oils were investigated. Three combinations of catalysts HG2 / RuH, UM42 / RuH and UM42 / PdBr showed different products distributions of olefins, esters and diesters. The formation of three equilibrium distributions could be observed when transesterified olive oil was used as substrate. When the substrate was transesterified sunflower oil, no equilibrium mixture was obtained due to the formation of conjugated double bonds. The olefin metathesis catalyst UM42 requires activation, which occurred in the presence of both isomerization catalysts RuH and PdBr. Two mechanistic pathways have been proposed to explain these observations. The activation of UM42 by RuH or PdBr was explained through the formation of the complexes B and C or B and E, respectively. The 14 electron complex B is suggested to be metathesis active, while the complexes C and E may form species able to perform olefin isomerization.

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Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES
Considering the diversity of theories available on the treatment of metaphor, we have two methodological options of study: either we approach it under the foundations of one area and analyze the object from the constructed properties within the scope of the approach; or we construct an interface repackaging, in which we put into play complex properties that delimit a third object built on the borderlines of disciplines in dialogue (CAMPOS, 2007). In the study that we propose, we illustrate this second approach, putting into dialogue the foundations of Linguistics, especially Pragmatics - via Grice's Theory of Implicatures (1967; 1975) and via Relevance Theory, by Sperber and Wilson (1986; 2008) and Wilson and Sperber, (2012) - and Psicolinguistics (GLUCKSBERG et al., 2007; BOWDLE and GENTNER, 2005), on the one hand; and, on the other, Neuroscience, through a qualitative meta-analysis constructed by the study of twenty fMRI experiments, from which the circuitry of the neurological processing of the metaphor is described. In this meta-analysis, we have tried to elucidate the nature of the theoretical approach and its implications in the design of the experiments and in the results achieved, in order to collect elements to compose the meta-theoretical approach of the interface that we proposed. In a second moment, then, we elevate the properties constructed in the scope of each area to the condition of meta-theoretical properties of the metaphor, with the purpose of putting into dialogue theories with distinct granularity and of proposing an alternative to the mapping problem (POEPPEL, 2012) resulting from a study of this nature. We thus have constructed a third, more complex object by deepening the descriptive and explanatory potential of the treatment given to the metaphor. Therefore, we see that, from an interface approach, two consequences emerge: the first, epistemological, because we contribute in the debate about the properties of the metaphor theories in interface, from whose dialogue the revitalization of the foundations in dialogue results; the second, theoretical, because we also contribute to the debate about the properties of the metaphor itself. The proposed interface emphasizes the potential of such approaches by extending possibilities for new treatments of different objects of linguistic research, including the metaphor itself.
Considerando a diversidade de teorias que temos ? disposi??o sobre o tratamento da met?fora, temos duas op??es metodol?gicas de estudo: ou a abordamos sob os fundamentos de uma ?rea e analisamos o objeto a partir das propriedades constru?das dentro do escopo da abordagem; ou constru?mos uma roupagem de interface, em que colocamos em jogo propriedades complexas que delimitam um objeto terceiro constru?do nas fronteiras das disciplinas em di?logo (CAMPOS, 2007). No estudo que propomos, ilustramos essa segunda abordagem, colocando em di?logo fundamentos da Lingu?stica, em especial da Pragm?tica ? via Teoria das Implicaturas de Grice (1967; 1975) e via Teoria da Relev?ncia, de Sperber e Wilson (1986; 2008) e Wilson e Sperber, (2012) ? e da Psicolingu?stica (GLUCKSBERG et al., 2007; BOWDLE e GENTNER, 2005), de um lado; e, de outro, da Neuroci?ncia, por meio de uma meta-an?lise qualitativa constru?da pelo estudo de vinte experimentos com fMRI, a partir dos quais descreve-se a circuitaria do processamento neurol?gico da met?fora. Nessa meta-an?lise, procuramos elucidar a natureza da abordagem te?rica e suas implica??es no design dos experimentos e nos resultados alcan?ados, no intuito de recolhermos elementos para compor a abordagem metate?rica da interface que propusemos. Num segundo momento, ent?o, al?amos ? condi??o de propriedades metate?ricas da met?fora as propriedades constru?das no escopo de cada ?rea, com o prop?sito de colocar em di?logo teorias com granularidade distinta e de propor uma alternativa ao mapping problem (POEPPEL, 2012) decorrente de um estudo dessa natureza. Constru?mos, assim, um objeto terceiro, mais complexo, ao aprofundarmos o potencial descritivo e explanat?rio do tratamento dado ? met?fora. Dessa forma, verificamos que de uma abordagem na interface emergem duas consequ?ncias: a primeira, epistemol?gica, porque contribu?mos no debate sobre as propriedades das teorias da met?fora em interface, de cujo di?logo decorre a revitaliza??o dos pr?prios fundamentos em di?logo; a segunda, te?rica, porque tamb?m contribu?mos no debate sobre as propriedades da met?fora em si. A interface proposta evidencia o potencial de abordagens dessa natureza por ampliarem possibilidades de novos tratamentos a diferentes objetos de investiga??o lingu?stica, entre os quais a pr?pria met?fora.

Boston University. University Professors Program Senior theses.
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2031-01-02

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Em face dos controversos debates em torno do conceito de literatura negra ou afrobrasileira, o presente trabalho visa ao estudo de textos críticos e literários metalinguísticos dos autores afrobrasileiros Oswaldo de Camargo, Luiz Silva - Cuti e Márcio José Barbosa, afim de apresentar as suas respectivas proposições acerca da arte que produzem. Foram analisados escritos literários ou não que de algum modo, apresentam concepções de literatura negra ou afrobrasileira. Conclui-se que são diversificadas as formas de entender a arte literária construída por afrobrasileiros. Nessa multiplicidade de apreciações, eles buscam a sua inserção no discurso da discurso da brasilidade e nesta, desejam acrescentar as suas vozes distanciadas da suposta homogeneidade nacional.

Fondée sur un corpus de 436 textes de recensions germanophones publiées dans cinq supports de presse généraliste lors du premier semestre 2012, cette étude porte sur le discours de la critique littéraire germanophone. Pour tenter d’identifier des traits constitutifs de la recension, trois axes de recherche sont envisagés : les perspectives textuelle, discursive et métatextuelle. Traditionnellement conçue à partir de la fonction, la notion de texte est considérée ici sous l’angle de la forme. En recourant aux notions de séquences et de périodes, élaborées dans le cadre de la linguistique textuelle, cette étude identifie un réservoir de formes à l’origine de la composition et de la configuration des recensions. Par ailleurs, la perspective discursive permet d’appréhender le sujet énonciateur des recensions comme un lieu de transition de la parole et du savoir. Le critique littéraire s’octroie, en effet, une position institutionnelle qui marque son rapport au savoir afin d’exercer une influence optimale sur le lecteur. L’enjeu est de repérer les marqueurs discursifs qui fondent cette visée argumentative. Enfin, la perspective métatextuelle oblige à concevoir la recension dans son rapport au texte source. Véritable dialogue avec l’œuvre critiquée, la critique exploite explicitement des stratégies empruntées aux discours littéraire et journalistique. Des procédés de reprise textuelle tels que la reformulation, la citation, l’allusion ou la contamination menacent de saper le métatexte pour en faire un hypertexte. Ces trois axes permettent d’aborder la recension en tant que genre, à l’interface entre texte et discours. Les résultats confirment l’idée que le genre doit être abordé non pas dans une perspective statique, comme une liste d’invariants, mais dans une perspective dynamique, comme le résultat de l’interférence de plusieurs genres discursifs. Enfin, c’est une meilleure compréhension de la production et de la réception des recensions qui est en jeu
Based on a corpus of 436 texts of German book reviews published in five newspapers of non-specialized press during the first half of the year 2012, this study investigates the discourse of German literary criticism. To try and identify constituent characteristics of the review, three areas of research are envisaged: the textual, discursive and metatexual perspectives. Traditionally conceived with regards to function, the notion of text is considered here in terms of shape. By considering the notions of sequences and periods, developed within the text linguistics, this study identifies a reservoir of forms which underpin the composition and the configuration of the reviews. Besides, the discursive perspective allows us to get a sense the speaking subject of the reviews as a transition for speech and knowledge. The literary critic actually benefits from putting himself in an institutional position that marks his/her relation to knowledge in order to have the best influence on the reader. The challenge is to identify possible linguistic markers which serve this argumentative approach. Finally, the metatextual perspective obliges us to conceive the review in its relationship with the source text. The book review is a real dialogue with the criticized book, the criticism explicitly exploits strategies borrowed from the literary and journalistic speeches. Textual processes of repetition such as reformulation, quotation, allusion or contamination threat to undermine the metatext into a hypertext. These three axes allow to approach the review as a genre, in the interface between text and discourse. The results confirm the idea that the genre must be approached not in a static way, as a list of invariants, but in a dynamic way, as the product of the interference of several discursive genres. Finally, what is at stake is a better understanding of the production and of the reception of the reviews

Orientador: Regina Buffon
Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica
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Resumo: Os catalisadores heterogêneos à base de rênio constituem-se importantes sistemas na metátese de ésteres insaturados provenientes dos óleos vegetais. No entanto, os sistemas heterogêneos à base de rênio são ativos na metátese de olefinas funcionalizadas somente se forem combinados com um promotor do tipo SnR4 ou PbR4. Acredita-se que o promotor tem a função de formar a espécie metal-alquilideno (no caso, rênio-alquilideno) que desencadeia o ciclo catalítico. Entretanto, ainda não é compreendido o mecanismo de formação dos promotores na superfície dos sistemas de óxidos. O objetivo principal desse trabalho consistiu em tentar identificar, através da RMN-C no estado sólido, a possível formação da espécie rênio-alquilideno sobre a superfície do sistema de óxidos (2%)Re2O7/(7,5%)B2O3/SiO2-Al2O3(75%) após a interação deste com o organometálico enriquecido com C, Sn( CH3)4. Buscou-se também caracterizar as interações entre os organometálicos (SnBu4, Bu3SnH e Bu2SnH2) com o mesmo sistema de óxidos através das técnicas de RMN-C no estado sólido e de espectroscopia no infravermelho. E finalmente, procurou-se identificar a estrutura do mesmo sistema de óxidos através das técnicas de RMN Al e Si no estado sólido, espectroscopia no infravermelho e difração de raios X
Abstract: Heterogeneous rhenium catalysts are importants systems for the metathesis of unsaturated esters obtained from vegetables oils. Nevertheless, the heterogeneous rhenium systems are actives for the metathesis functionalized olefins when combined with a promoter like SnR4 or PbR4. It is believed that it leads to the formation of the alkylidene species that will start the catalytic cycle. However, the role of the promoters on oxide system surface is not well understood. The main goal of this work was to identify, via CP-MAS C NMR, a possible rhenium-alkylidene species formed by the reaction between Sn(CH3)4 and (2%)Re2O7/(7,5%)B2O3/SiO2-Al2O3(75%). The reactions of SnBu4, Bu3SnH e Bu2SnH2 with (2%)Re2O7/(7,5%)B2O3/SiO2-Al2O3(75%) were also investigated by CP-MAS C NMR and in situ FT-IR experiments. Finally, the structure of the (2%)Re2O7/(7,5%)B2O3/SiO2-Al2O3(75%) material was studied by Al and Si MAS NMR, FT-IR and X ray diffraction
Mestrado
Quimica Inorganica
Mestre em Química

A versatilidade da reação de metátese de olefinas foi explorada no presente trabalho de duas formas diferentes. Em ambas as formas buscou-se novas alternativas para a metátese de olefinas catalisada por complexos de rutênio. Na primeira parte do trabalho, ácido maleico (MA-H – do inglês Maleic acid) é descrito como uma alternativa ao uso de ésteres de acrilato na metátese cruzada (CM – do inglês crossmetathesis) para preparar compostos carboxílicos α,β-insaturados. Portanto, a reação entre oleato de metila (MO – do inglês methyl oleate) com MA-H foi investigada, otimizando diversos parâmetros de reação como o método de purificação do MO, razão MO:MA-H, temperatura, tempo, concentração e tipo de (pre)-catalisador. Todas as reações foram monitoradas por um período de 70 minutos. Quatro (pré)-catalisadores de rutênio comercialmente disponíveis foram utilizados. Os (pré)-catalisadores de Grubbs (GII) e Hoveyda-Grubbs (HGII) de segunda geração apresentaram os melhores resultados. Reações de CM entre MO e MA-H usando 0.05 mol% de GII ou HGII resultaram em conversões de 92 e 88 % e seletividade para os produtos de metátese cruzada de 89 e 78 %, respectivamente. Estudos adicionais utilizando ácido acrílico (AA-H – do inglês acrylic acid) e acrilato de metila (AA-Me – do inglês methyl acrylate) foram efetuados e mostraram que para o complexo GII, o qual dissocia um ligante fosfina (PCy3) em sua etapa de iniciação, a formação de espécies propagantes do tipo rutênio-metilideno acarretam em um efeito detrimental para a reação (a formação de espécies propagantes rutênio-metilideno é totalmente evitada utilizando MA-H como substrato). Além disso, para os respectivos ésteres, grupos alcóxidos volumosos prejudicam ambos os rendimento e conversão da reação. Posteriormente, óleos vegetais insaturados foram investigados como alternativa ao uso de MO na reação com MA-H. Nas reações utilizando óleos vegetais observou-se que o uso de tais substratos não acarretam efeitos detrimentais para a reação. A reação entre GII com MA-H foi investigada por espectroscopia de ressonância magnética nuclear (RMN de 1H e de 31P{1H}) em THF-d8 à 20 ºC. A reação ocorreu lentamente por um período de 7 horas com cinética observada de primeira ordem. O consumo de GII com a formação concomitante de um novo complexo alquilidênico foi observado. Os espectros de RMN 13C{1H}, 1H-13C HSQC e 1H-13C HMBC claramente mostraram a formação de um complexo rutênio-carbeno enoico. A espécie rutênioxcarbeno enoico é a espécie propagante da reação de CM entre MO e MA-H e também de outras reações de metátese de olefinas envolvendo acrilatos. Esta foi a primeira vez que tal espécie foi observada via reação de metátese e caracterizada espectroscopicamente Na segunda parte do trabalho, rotas sintéticas alternativas para a síntese do (pré)-catalisador de Hoveyda-Grubbs de segunda geração (HGII) que não envolve o uso de fosfinas de sacrifício e diazo compostos foi investigada. Três precursores de rutênio foram estudados na reação com álcool 1,1-difenilpropargílico como fonte do alquilideno. O precursor trans-RuCl2(py)4 mostrou-se inerte frente à reação com o álcool propargílico. A reação do precursor dimérico de rutênio [RuCl2(p-cimeno)]2 com os carbenos N-heterocíclos IMes (1,3-bis(2,4,6-trimetilfenil)imidazol-2-ilideno) e H2IMes (1,3-bis(2,4,6-trimetilfenil)-4,5-dihidroimidazol-2-ilideno) resultou na formação dos complexos monoméricos RuCl2(p-cimeno)IMes (Ru-35a) e RuCl2(p-cimeno)H2IMes (Ru-35b), respectivamente, os quais decompôem-se em solução com perda do ligante p-cimeno. Os compostos Ru-35a,b reagem com álcool 1,1-difenilpropargílico, porém, observou-se que os produtos se decompuseram durante a reação, impossibilitando a isolação dos produtos. O precursor cis-RuCl2(DMSO)4 reagiu com álcool 1,1- difenilpropargílico resultando em uma mistura complexa de produtos, a qual não foi possível isolar e analisar adequadamente. Nenhuma das rotas usando os três precursores de rutênio investigados resultou no desenvolvimento de uma nova estratégia sintética para a síntese de HGII.
The versatility of the olefin metathesis reaction was explored in the work described herein, pursuing two different strategies for new alternatives in the rutheniumcatalyzed reaction. In the first part is described the use of maleic acid (MA-H) as an alternative to the use of acrylate esters in the cross-metathesis (CM) to produce α,β- unsaturated carboxylic compounds. Therefore, the reaction of methyl oleate (MO) with MA-H was investigated, optimizing a series of parameters such as the MO purification method, MO:MA-H ratio, temperature, time, and concentration. All reactions were monitored over the course of 70 minutes. Commercially available ruthenium metathesis (pre)-catalysts were employed. The second-generation Grubbs (GII) and Hoveyda- Grubbs (HGII) metathesis (pre)-catalysts displayed the best results. The CM of MO with MA-H using 0.05 mol% of GII or HGII resulted in conversions of 92 and 88 % and selectivity towards the CM products of 89 and 78%, respectively. Further studies employing acrylic acid (AA-H) and methyl acrylate (AA-Me) with the phosphinecontaining (pre)-catalyst GII showed that the formation of a ruthenium-methylidene propagating specie has a detrimental effect on the outcome of the reaction. Such specie is completely avoided when MA-H is used as CM-partner. Moreover, bulkier alkoxysubstituents also jeopardize both conversion and yield of the reaction. Additionally, the use of unsaturated vegetable oils was investigated as an alternative to the direct use of MO in the reaction with MA-H. The use of vegetable oils as substrates was found to have no detrimental effect on the reaction. The reaction of GII with MA-H was investigated by NMR spectroscopy (1H and 31P{1H}) in THF-d8 at 20 ºC, which proceeded slowly over the course of 7 hours with observed first order kinetics. Disappearance of GII with concomitant formation of a new alkylidenic complex was observed. 13C{1H} NMR and 2D techniques (1H-13C HSQC and 1H-13C HMBC) confirmed the formation of a ruthenium-enoic carbene complex. A ruthenium-enoic carbene intermediate is the propagating specie of the CM reaction of MO with MA-H and also of other olefin metathesis reactions involving acrylates. This was the first time such specie could be observed and characterized spectroscopically. The second part of this work investigated alternative synthetic routes to the second-generation Hoveyda-Grubbs (pre)-catalyst (HGII) that avoid the use of sacrificial phosphines and diazo compounds as the alkylidene source. Three different ruthenium precursors were applied in the reaction with 1,1-diphenylpropargyl alcohol (source of the alkylidene ligand). The precursor trans-RuCl2(py)4 was found to be inert towards the reaction with the propargylic alcohol. Reaction of the dimeric precursor [RuCl2(pcymene)] 2 with the N-heterocyclic carbenes IMes (1,3-bis(2,4,6- trimethylphenyl)imidazol-2-ylidene) and H2IMes (1,3-bis(2,4,6-trimethylphenyl)-4,5- dihydroimidazol-2-ylidene) afforded the corresponding monomeric complexes RuCl2(pcymene) IMes (Ru-35a) and RuCl2(p-cymene)H2IMes (Ru-35b), which decompose in solution with loss of the p-cymene ligand. Both compounds Ru-35a,b reacted with 1,1- diphenylpropargyl alcohol but decomposition occurred during the reaction, which circumvented the isolation of the corresponding products. The precursor cis- RuCl2(DMSO)4 reacted with 1,1-diphenylpropargyl alcohol but formed a complex mixture of products, which did not allow the isolation of the desired compound. Independent of the ruthenium precursor, none of the routes investigated resulted in the development of a new synthetic strategy for the synthesis of HGII.

A queima de combustíveis fósseis gera problemas ambientais como o aquecimento global. Além disso, considerando que o petróleo é uma fonte não renovável e seu esgotamento está previsto para o futuro, pesquisas vêm sendo realizadas para a produção de biocombustíveis e materiais de origem renovável. Nesse trabalho foi desenvolvida uma nova metodologia para a produção de biocombustíveis e insumos renováveis através de reações de metátese de olefinas utilizando os catalisadores de Grubbs/Rutênio. Dois diferentes tipos de substratos foram utilizados nessa metodologia: óleos vegetais e ésteres de ácidos graxos obtidos por transesterificação e esterificação. Foram realizadas reações de metátese cruzada entre esses substratos e etileno (etenólise) para a produção de olefinas terminais, que são insumos de grande utilização na indústria química. Os efeitos da influência da temperatura, pressão, tempo, catalisador, adição de tolueno e razão substrato:catalisador foram avaliados para essas reações. A produção de biogasolina/bioquerosene foi testada a fim de se avaliar a possibilidade de obtenção desses biocombustíveis através das reações de transesterificação e hidrogenação desses produtos contendo olefinas terminais. A avaliação das conversões obtidas nas reações de etenólise dos dois tipos de substratos foi realizada por 1H-RMN e comparada com a caracterização por GC-MS. Foram obtidos os produtos das reações de etenólise contendo olefinas terminais para os dois substratos testados e conversões moderadas foram obtidas. No estudo das reações utilizando óleo de oliva foram obtidos conversões de até 34% quando uma menor razão substrato:catalisador foi aplicada. Utilizando ésteres de ácido graxo a maior conversão obtida foi de 48% quando o oleato de metila comercial foi utilizado. As reações de hidrogenação ocorreram com conversão total das olefinas internas e terminais a compostos saturados. Foram obtidos biocombustíveis contendo até mais de 40% de biogasolina/bioquerosene em sua formulação.
The combustion of fossil fuels causes environmental problems like global warming. Furthermore, considering that petroleum is a non-renewable fuel source implies that its reserves will run out in the near future. As a consequence, intensive research efforts are in progress for the production of biofuels and renewable raw materials, necessary for establishing biorefineries. This thesis addresses a novel methodology for the production of biofuels and renewable raw materials by ruthenium-catalyzed olefin metathesis reactions as key catalytic reaction. Two different substrate types were used in this methodology: vegetable oils and fatty acid esters obtained by transesterification and esterification reactions. Cross-metathesis reactions were performed between these substrates and ethylene (ethenolysis) for the production of terminal olefins, which are raw materials of extensive use in the chemical industry. The influence of temperature, pressure, time, catalyst, solvent additive/solubility and substrate:catalyst ratio was evaluated for these reactions. Transesterification and hydrogenation of the terminal olefin products was performed to produce novel biofuels in the range of biogasoline and biokerosene. The conversions in ethenolysis reactions of both substrates were determined by 1H-RMN and GC-MS. For the two substrates tested in the ethenolysis reaction, products containing terminal olefins were obtained with moderate conversions. Olive oil ethenolysis was achieved with a conversion of up to 34% when a lower substrate:catalyst ratio was applied. Using fatty acid esters, the highest conversion of 48% was obtained with commercial methyl oleate. Complete conversions of the internal and terminal olefins were achieved in the hydrogenation reactions. Biofuels were obtained containing up to more then 40% of biogasoline/biokerosene in its formulation.

In this work, the reactions of cross-metathesis of substrates of natural origin (anethole, isoeugenol and isosafrole) were studied with the following acrylates: methyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate in a solvent-free system, with excess acrylate and employing the catalysts: Grubb-Nolan [dichloro (2,5-dimesitylimidazolyl-ilidene) (tricyclohexylphosphine) benzylideneruthenium (II)] and Hoveyda-Grubbs second generation [dichloro (3,4-dihidro-dimesitylimidazolyl-ilidene) 2- isopropoxihenylilideneruthenium (II)] These reactions were aimed for the synthesis of products which have significant commercial applications, the cinnamates, UV absorbing molecules and ferulates, molecules with antioxidant properties, anti-inflammatory and anticancer. The reactions performed using the Grubbs-Nolan catalyst in a system without solvent and with an excess of acrylate occur only with the addition of phenols. Phenols improve the activity the system and minimize the formation of homodimers. The phenols tested were: 2-tert-butylphenol, 4-tert-butylphenol and 2,6 tert-butylphenol. The 4-tert-butylphenol showed the best performance. Under the best conditions, yields for cinnamates and ferulates from 89% to 99% were obtained by using 2.8 mol% [dichloro (2,5-dimesitylimidazolyl-ilidene) (tricyclohexylphosphine) benzylideneruthenium (II)], 4 hours of reaction at 70 °C and with the addition of 500 equivalents of 4-tert-butylphenol in the reactions in the presence of anethole and isosafrole and of 18 equivalents of this phenol in the presence isoeugenol. The reactions using the second generation Hoveyda-Grubbs catalyst were carried out without addition of phenol. Under the best conditions, the ferulates and cinnamates were obtained in yields of 91% and 100% using 0.5 mol% [dichloro (3,4-dihidro-dimesitylimidazolyl-ilidene) 2- isopropoxihenylilideneruthenium (II)] in solvent-free system, with an excess of acrylate and 4 hours of reaction at 70 °C. By using 0.1 mol% of this catalyst under the same reaction conditions above yields of 73% to 88% for cinnamates and ferulates were obtained. The cross-metathesis of the propenyl benzenes (anethole, isosafrole and isoeugenol) with methyl, ethyl and 2-ethylhexyl acrylates is a short, highly efficient and sustainable route for the synthesis.
Neste trabalho foram estudadas as reações de metátese cruzada dos substratos de origem natural (anetol, isosafrol e isoeugenol) com os seguintes acrilatos: acrilato de metila, acrilato de etila e acrilato de 2-etil-hexila em sistema isento de solvente, com excesso de acrilato e empregando os catalisadores: Grubb-Nolan [dicloro (2,5-dimesitilimidazolil-ilideno) (tricicloexilfosfina) benzilideno-rutênio II] e Hoveyda-Grubbs segunda geração [dicloro (3,4-dihidro-dimesitilimidazolil-ilideno) .2- isopropoxi benzilideno-rutênio II]. Essas reações foram realizadas visando a síntese de produtos que possuem aplicações comerciais importantes, os cinamatos, moléculas absorventes de radiações UV e os ferulatos, moléculas com propriedades antioxidante, anti-inflamatória e anticancerígena. As reações realizadas empregando o catalisador de Grubbs-Nolan em sistema sem solvente e com excesso de acrilato ocorrem somente com adição de fenóis. Os fenóis melhoram a atividade do sistema e minimiza a formação dos homodímeros. Foram testados os fenóis: 2-terc-butilfenol, 4-terc-butilfenol e 2,6 terc-butilfenol. O 4-terc-butilfenol apresentou o melhor desempenho. Nas melhores condições, foram obtidos rendimentos para os cinamatos e ferulatos de 89% a 99% com a utilização de 2,8 mol% de [dicloro (2,5-dimesitilimidazolil-ilideno) (tricicloexilfosfina) benzilideno-rutênio II], 4 horas de reação, a 70 ºC e com a adição de 500 equivalentes de 4-terc-butilfenol nas reações em presença do anetol e isosafrol e as em presença do isoeugenol de 18 equivalentes desse fenol. As reações utilizando o catalisador Hoveyda-Grubbs segunda geração foram realizadas sem necessidade de adição de fenóis. Nas melhores condições, os cinamatos e ferulatos foram obtidos com rendimentos de 91% a 100% utilizando 0,5 mol% de [dicloro (3,4-dihidro-dimesitilimidazolil-ilideno) .2- isopropoxi benzilideno-rutênio II], em sistema isento de solvente, com excesso de acrilato e 4 horas de reação a 70 ºC. Com a utilização de 0,1 mol% desse catalisador, nas mesmas condições reacionais acima, foram obtidos rendimentos de 73% a 88% para os cinamatos e ferulatos. A metátese cruzada das olefinas propenil aromáticas (anetol, isosafrol e isoeugenol) com os acrilatos: de metila, de etila e de 2-etil-hexila é uma rota sucinta, altamente eficiente e sustentável para síntese de cinamatos e ferulatos, produtos de interesse para Química Fina.

The manos and metates of Santa Rita Corozal, Belize are analyzed to compare traditional maize-grinding types to the overall assemblage. A reciprocal, back-and-forth grinding motion is the most efficient way to process large amounts of maize. However, rotary movements are also associated with some ground stone implements. The number of flat and trough metates and two handed manos are compared to the rotary-motion basin and concave type metates and one-handed manos to determine predominance and distribution. Flat is the predominant type and, together with the trough type, these grinding stones make up the majority of metates at the site. Manos are highly fragmented, but the two-handed variety is more common among those fragments able to be identified. While this would at first glance support a fully maize dependent subsistence, the presence of two additional non-reciprocal motion metate types and the fact that the trough metates are clustered in one sector of the site suggest that, in addition to maize, significant processing of other foods also occurred in association with these grinding stones.
ID: 030423021; System requirements: World Wide Web browser and PDF reader.; Mode of access: World Wide Web.; Thesis (M.A.)--University of Central Florida, 2011.; Includes bibliographical references (p. 96-110).
M.A.
Masters
Anthropology
Sciences

Este trabajo hace una propuesta metodológica a partir del uso de las geotecnologías, para que los adultos mayores de una localidad rural y a partir del conocimiento que tienen de su entorno, puedan aportar soluciones para atender sus necesidades de salud, abasto, desarrollo social y familiar.

Orientador: Luiz Carlos Dias
Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica
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Resumo: O capítulo 1 relata as sínteses da macrolactona da migrastatina 11 e da macrolactona análoga 62a. A macrolactona da migrastatina é o composto que apresenta a maior atividade de inibição de migração de células tumorais in vitro dentre os compostos da família da migrastatina até hoje sintetizados. A macrolactona 62a, ainda inédita na literatura, é epímero em C8 da macrolactona 62b sintetizada pelo grupo do Professor Danishefsky em 2004 e apresenta atividade de inibição semelhante à macrolactona 11. Além disso, foram realizados estudos visando à síntese da macrolactona 124, epímero da macrolactona 11. Paralelamente, em colaboração com a Farmoquímica Cristália e o grupo do Professor Adriano Andricopulo, do IF/USP de São Carlos, foram realizados testes de avaliação biológica de diversos compostos sintetizados neste trabalho com o intuito de gerar novas substâncias químicas bioativas candidatas a novos fármacos no tratamento do câncer de mama. O capítulo 2 relata a síntese e aplicação de alguns substratos contendo grupos funcionais que ainda não haviam sido testados frente à reação de metátese de alcinos utilizando um novo catalisador de molibdênio. Este projeto foi desenvolvido no laboratório do Professor Alois Fürstner, no Instituto Max-Planck, em Mülheim an der Ruhr ¿ Alemanha. Além disso, um precursor do fragmento B das Latrunculinas A e B foi sintetizado em grande escala, fornecendo material para subsequentes estudos químicos e biológicos
Abstract: Chapter 1 describes the syntheses of macrolactones 11 and 62a. Macrolactone 11 presents the best tumor cell migration inhibitory effect among the compounds of the migrastatin family synthesized so far. Macrolactone 62a, not described in the literature, is the C8-epimer of macrolactone 62b, which was synthesized by Professor Danishefsky¿s group in 2004 and shows similar antitumor activities when compared to macrolactone 11. Studies aiming at the synthesis of macrolactone 124, epimer of macrolactone 11, were also performed. Besides, in collaboration with Farmoquímica Cristália and Professor Andricopulo¿s group (IF/USP, São Carlos), biological assays of several compounds synthesized in this work were carried out, with the purpose of developing new bioactive chemical substances which may soon be employed in the manufacturing of novel drugs in the treatment of breast cancer.Chapter 2 describes the syntheses of new substrates for applications in Mo-catalyzed RCAM. This project was carried out in Professor Fürstner¿s laboratory, at Max-Planck Institute, in Mülheim an der Ruhr ¿ Germany. In this part of the work, a Latrunculin A and B fragment precursor was also synthesized in large scale to provide further material for new biological and chemical studies
Doutorado
Quimica Organica
Doutor em Ciências

L'aparició d'una química organometàl·lica basada en els metalls de transició de la primera fila ha guanyat protagonisme amb el propòsit de transformar la química en una disciplina més respectuosa amb el medi ambient. La metàtesi d'olefines és una de les reaccions més importants en la síntesi orgànica, ja que permet la formació de nous enllaços C=C. La reacció està catalitzada per carbens de ruteni o molibdè, però el alt cost i la toxicitat d’aquests metall impedeixen en bona part les seves aplicacions industrials. Per tant, la reacció de la metàtesi d'olefines és un exemple paradigmàtic en què l’obtenció d’un catalizador basat en ferro, desitjat des de fa temps, pot tenir conseqüències importants. Aquesta tesi és una exploració teòrica, que utilitza mètodes DFT, amb la finalitat d'entendre com la naturalesa dels lligands, l'esfera de coordinació i l'estat formal d'oxidació del metall han de ser ajustats per aconseguir un catalitzador de metàtesi d'olefines basat en el ferro. Per fer-ho, es presenta un estudi sobre l'estructura electrònica de complexos de ferro i la seva reactivitat amb olefines i una recerca in-silico sobre possibles lligands que es poden utilitzar per produir aquest catalitzador. L'estudi de la reactivitat dels carbens de ferro prèviament publicats a la bibliografia mostra que els complexos amb una alta coordinació eviten la formació del metalociclobutà, impedint així la reacció de metàtesi, donant lloc a la ciclopropanació mitjançant una ruta de transferència de carbè concertada. D’altra banda, els que presenten una baixa coordinació mostren un estats fonamentals diferents del singlet i també produeixen productes de ciclopropanació, però en aquest cas per una via biradicalària de transferència de carbè. La cerca in-silico de lligands auxiliars per proposar un complex de ferro-carbè per millorar la ometàtesi d’olefines sobre la ciclopropanació ha demostrat que els lligands auxiliars tridentats que contenen σ-donants grups són bons candidats per a tals objectius, ja que proporcionen carbens de ferro en l'estat singlet i permeten la formació del metalociclobutà intermedi, en estat singlet. Tanmateix, una via per a la ciclopropanació per eliminació reductiva del metalociclobutà encara té barreres més baixes que la cicloreversió per a la metàtesi d'olefines. En el cas dels carbens de ferro pentacoordinats, la reducció per dos electrons al centre metàl·lic sembla ser la millor manera de promoure el carbè i el metalociclobutà a l'estat singlet. Els desavantatges són que aquests complexos estan molt coordinats, amb 18 electrons, evitant la coordinació d'una olefina entrant, impedint així la formació de metalociclobutà. Una vegada més, la ciclopropanació passa a través d'un mecanisme de transferència de carbè per passos. Una anàlisi general de la força dels enllaços dobles del carbens de metalls mostra una correlació inversa amb l'estabilitat termodinàmica dels productes de ciclopropanació, el que indica que lligands que reforcen l'enllaç ferro-carbè són adequats seguir la recerca per un catalitzador de ferro para metàtesi d’olefines.
The advent of an organometallic chemistry based on the earth-based first-row transition metals has been gaining attention within the purpose of transform chemistry in a more environmentally friendly discipline. Olefin metathesis is one of the most powerful reactions in organic synthesis as it allows the formation of new C=C double bonds. The reaction is catalyzed either by ruthenium or molybdenum metal carbenes whose cost and toxicity partially prevents their industrial applications. Therefore, the Olefin Metathesis reaction is a paradigmatic example in which the achievement of the long desired Fe-based catalyst can potentially have breakthrough consequences. This Thesis is a theoretical exploration, using DFT methods, aiming at understanding how the nature of the ligands, the coordination sphere and the formal metal oxidation state should be tune to achieve an olefin metathesis catalyst based on iron. To do so, we present here a study about the electronic structure of iron-complexes and its reactivity with olefins and an in-silico design search about possible ancillary ligands that can be used to produce this catalyst. Reactivity’s study of iron carbenes previously reported in the literature shown that high-coordinate complexes avoid the formation of the metallacyclobutane, therefore impeding the olefin metathesis reaction, resulting in cyclopropanation by a concerted carbene transfer path. Whereas the low-coordinated iron-carbenes studied show a non-low-singlet behavior, and also results in cyclopropanation products, but in this case by a carbene-transfer stepwise birradical pathway. In-silico search for ancillary ligands to propose an iron-carbene complex to improve olefin-metathesis over cyclopropanation, has shown that ancillary tridentate ligands containing σ-donating ligands are good candidates for such goals, since they provide iron-carbene in the singlet state and allow the formation of the intermediate metallocyclobutane, in the singlet state. However a pathway for cyclopropanation by reductive elimination from the metallocyclobutane still has lower barriers than the cycloreversion for olefin metathesis. For the case of pentacoordinate iron-carbenes, the reduction by two electrons in the metallic center seems to be the best way to promote the carbene and the metallocycle in the singlet state. The disadvantages are that these complexes are high-coordinated with 18 electrons, preventing the coordination of an incoming olefin, therefore avoiding the metallacyclobutane formation. Again, cyclopropanation takes through a carbene stepwise carbene transfer mechanism. An overall analysis regarding metal-carbene double bond strength showed an inverse correlation with the thermodynamic stability of the cyclopropanation products, indicating that ligands that reinforces the iron-carbene bond is a way to be followed in the search for a olefin metathesis iron-based catalyst.

Orientador: Ronaldo Aloise Pilli
Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química
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Resumo: Este trabalho trata de estudos visando à síntese estereosseletiva do alcalóide 275A (18, Figura 1). Esse alcalóide foi isolado por Daly e colaboradores da pele de pequenas rãs venenosas neotropicais da família Dendrobatidae em 1986. Sua estrutura possui um núcleo 1-azabiciclo[5.3.0]decano de grande importância sintética. Para construção desse núcleo utilizamos, principalmente, as reações de a-amidoalquilação e de metátese de olefinas de fechamento de anel (RCM), tendo como reagente inicial a (S) prolina (57) Esquema1
Abstract: This work consists in studies toward the stereoselective synthesis of alkaloid 275A (18, Figure 1). This alkaloid was isolated by Daly and co-workers from the skin of neotropical poison little frogs of Dendrobatidae family in 1986. His structure has an 1-azabicyclo[5.3.0]decane nucleus of great synthetic importance. To construct this nucleus we used, mainly, a-amidoalkylation reactions and ring close metathesis (RCM), starting with (S) proline (57, Scheme 1)
Mestrado
Quimica Organica
Mestre em Química

Denna studie handlar om variation i skriven meänkieli med fokus på variation i ett specifikt drag, h i efterstavelsen (t.ex. saunhaan > sauhnaan 'till bastun'). Tidigare forskning har visat att detta språkdrag påträffas med omfattande variation efter ett särskilt mönster i talspråket (t.ex. Mantila 1992, 2010; Vaattovaara 2009). Syftet med denna studie är att undersöka om, och i vilken omfattning, det mönster som beskrivits för det talade språket också påträffas i skriven text på meänkieli. Studien föranleds av det faktum att meänkieli för närvarande befinner sig i en standardiseringsprocess. h i efterstavelsen i talat språk utgör ett komplext system, som kan uppfattas av vanliga språkanvändare som ”svårt att beskriva”. Hur som helst har tidigare forskning indikerat att användningen av h i talat språk är ganska systematiserat och ett mönster för variationen har utvecklats i en bestämd riktning över tid. Med tanke på denna studie är det av intresse att undersöka om mönstret är liknande i skriftlig form, det vill säga om de enskilda författarna i den undersökta korpusen använder sig av ett liknande system för h i sina litterära verk. Studien har inte som syfte att diskutera språkplanering eller principer för standardisering, utan syftet är att skapa en helhetsbild av språklig variation i användningen av h i skriftspråket. Korpusen består av 43 böcker av 18 olika författare från tre olika decennier (1980–2000). Från varje publikation är de första 5250 orden excerperade om verket innehåller fler ord (barnböckerna, som är kortare och till antalet 18, har excerperats i sin helhet.) Studiens primära fokus besvaras med hjälp av frågorna huruvida det förekommer variation mellan de olika författarna, och vilken typ av variation som förekommer inom de texter varje enskild författare skrivit, även över tid betraktat. Syftet med studien är att avslöja om variationsmönster eventuellt sprider sig, eller om mönstret indikerar lika användningssätt mellan de enskilda författarna. Enligt sociolingvistiska teorier om språklig förändring borde en s.k. undersökning i verklig tid över flera decennier visa huruvida en pågående förändring är på gång. Hypotesen för denna studie (huvudsakligen på basis av Mantila 2010) är, att ett liknande system som påträffas i talspråket också påträffas i skriven form. h i efterstavelsen har en historisk utveckling med många förändringar och är ur ett morfologiskt och fonologiskt perspektiv ett mångfacetterat språkdrag. Studien fokuserar enbart på de sex olika lingvistiska positioner där den metatetiska varianten av h i efterstavelsen kan förekomma, vilket alltid sker i samband med en tonande konsonant exempelvis på följande sätt: 1. Stockholmhiin > Stockholhmiin 'till Stockholm', 2. koulhuun > kouhluun 'till skolan', 3. korjaamhaan > korjaahmaan 'för att städa', 4. Pajalhaan > Pajahlaan 'till Pajala', 5. istumhaan >  istuhmaan 'för att sitta', 6. ymmärtänheet > ymmärtähneet 'har förstått'). Tidigare forskning har ansett denna specifika variant av h med metates vara ”ett varumärke för Tornedalen” och språkdraget har visat ett tydligt mönster för variation i Tornedalen. I denna studie speglas variationen av h‑metatesen i litteraturen på meänkieli mot tidigare forskningsresultat rörande talspråk, där språkdraget undersökts både i svenska och finska Tornedalen. Bengt Pohjanen (med det största antalet utgivningar), tillsammans med tre andra författare har undersökts närmare. Ett intressant resultat är att det förekommer relativt omfattande variation mellan dessa författare, samtliga bördiga från en och samma kommun, nämligen Pajala. I motsats till vad som hävdas i traditionell sociolingvistik stämmer inte här antagandet att författarnas härkomst skulle vara en styrande faktor i författarnas språkliga val. Det allra viktigaste resultatet i studien är att enskilda böcker har under de tre undersökta decennierna visat ett överraskande resultat i fråga om variation under 1980- och 1990-talet, men under 2000-talet har det mönster som påträffats i talat språk systematiserats och tagits i bruk på ett enhetligt sätt i litteraturen på meänkieli mer eller mindre hos samtliga författare. I positionerna 1–4 sker metates systematiskt i mellan 85 – 98 % av fallen, medan den i positionerna 5–6 endast påträffas i 0,8 – 1,4 % av fallen.
This study deals with variation in written Meänkieli, focusing on the variation of one specific feature, h in non-initial syllables (e.g. saunhaan, sauhnaan 'into sauna') which has been found to be rich in variation in spoken language according to earlier research (e.g. Mantila 1992, 2010; Vaattovaara 2009). The aim of this study is to investigate if, and to what extent, the variation patterns found in the spoken variety correspond to literature written in Meänkieli. The study is motivated by the fact that Meänkieli is currently undergoing standardization process. The variation of h in non-initial syllables forms a complex system in spoken language which, as a folk belief, is “difficult to describe”. However, earlier research has indicated that in the spoken language the use of the h is linguistically quite systematically structured and the variation patterns have developed in certain direction across time. In the interest of the present study is to investigate if the pattern is similar in the written form in the chosen corpus, that is, if the individual authors are implementing a similar system in their literary work. The principal aim of this study is not to deal with language planning and principles of language standardization but to form an overall picture of linguistic variation in the use of h in written language. The data consist of 43 books from 18 authors, and from three decades (1980–2000). From each publication, the first 5250 words are extracted into analysis, if the word count exceeds this number (children’s books, 18 included in the corpus, typically do not). The main interest of the current work lies in the question whether or not there is remarkable variation found between the different authors, and what kind of variation may appear within the texts authored by each individual author or across time. The aim of the study is to reveal if the variation patterns possibly scatter, or if the patterns indicate agreement between the individual authors. According to sociolinguistic theories of linguistic change, the so called real time investigation across the decades should indicate if there is an ongoing change. The hypothesis of the research (mainly on the basis of Mantila 2010) is that the variation pattern similar to spoken language is being adopted also in written forms. Since the h in non-initial syllables is both from the point of view of historical development as well as morphological and phonological conditions a very rich feature, this study focuses only on the six linguistic environments concerning the metathetic h variant (e.g. 1. Stockholmhiin > Stockholhmiin 'to Stockholm', 2. koulhuun > kouhluun 'to school', 3. korjaamhaan  > korjaahmaan 'to clean', 4. Pajalhaan > Pajahlaan 'to Pajala', 5. istumhaan >  istuhmaan ' to sit', 6. ymmärtänheet > ymmärtähneet 'have understood'), which always involves a voiced consonant. Earlier research has regarded this particular variant as “the trademark of Torne Valley” which has, on the present Finnish and Swedish side of the area, shown a clear pattern of variation. In this study, the variation of the metathetic h in Meänkieli literature is mirrored against earlier findings from the Torne Valley spoken data. Bengt Pohjanen (with the largest number of publications) together with three other authors have been investigated in more detail. An interesting finding is that there is relatively much variation among authors from one municipality, Pajala. Against the traditional sociolinguistic expectations, the origins of the authors is not a governing factor in linguistic choices. The main outcome of the whole analysis is that during the three decades investigated, individual books have indicated unexpected variation in the 1980s and 1990s, but by the 2000’s the same variation pattern found in spoken language has been more systematically and strongly adopted also into written Meänkieli by more or less all of the authors: in the phonotactic positions 1–4 the metathesis is systematic (85–98 %) while in the positions 5–6 only 0,8 to 1,4 %.

This thesis concerns with the literary theory of autobiography and its use for comics. The goal is to try to modify literary theory for comics and apply it in practical analysis. The fundamental theoretical framework constitutes of The autobiographical Pact by Philippe Lejeune and a theory of paratexts according to Gérard Genette. In practical analysis the thesis bases on the comparison of comics with literary work and uses the knowledge acquired in the theoretical part. The emphasis is put on designing of autobiographical pact and on para- and metatexts which are connected to both of the books. Klíčová slova anglicky Autobiography, autobiographic elements, comics, literature, paratext, metatext

La présente thèse se veut une relecture du fumisme en tant que concept et mouvement historique daté (années 1860-1880) et situé (la France), ou moment qui représente une économie de sens qui a bouleversé les habitudes perceptuelles et intellectuelles de la réception depuis la seconde moitié du dix-neuvième siècle. Selon la lecture habituelle du fumisme, les productions des poètes et artistes fumistes, qualifiées de « fumisteries », ne forment qu’un chapitre, ou une catégorie négligeable, de l’histoire littéraire. Cette histoire confond le fumisme en tant que mouvement littéraire éphémère avec les épisodes décadent et symboliste pour le réduire à un concours de mystifications de bourgeois par des bohèmes en marge par rapport à l’institution littéraire organisées par le comédien Sapeck et l’écrivain Alphonse Allais, tous deux nommés ironiquement chefs de « l’École fumiste » vers 1880. Or, en offusquant la conception positiviste du langage qu’elle lui applique afin de le réduire à une simple provocation sans but, et en assimilant Rimbaud aux « fumisteries » des « décadents », la critique littéraire nous donne l’outil principal de démystification du fumisme en tant que pratique ou mode de production d’une économie de sens. C’est cette économie qui constitue notre principal point d’intérêt. Contemporain des épisodes décadent et symboliste, le moment fumiste oblige la réception à reconfigurer la façon de produire du sens. Les productions fumistes (essentiellement des poèmes et des caricatures, comme dans l’Album zutique, notre corpus principal) sont fondées sur une économie du rébus. Exemplifiée par le sonnet de Rimbaud intitulé « Voyelles », cette économie, qui crée des « documents », des textes inséparables de leur matière, introduit l’économie artistique du vingtième siècle – en particulier, au mode de perception cinématographique tel que fabriqué par le fumiste Émile Cohl.
This thesis focuses on a particular period in literary history that goes under the name of fumism. This “fumist” moment, which occurred during the years 1860-1880 in Paris, introduces a new economy of meaning that, in the latter part of the nineteenth century, leads to a transformation in reader’s changing perceptual and intellectual habits. In the perspective of institutionalized literary history, critics conceive fumist productions as “fumisteries” (which might be rendered as “nonsense”) and lump this ephemeral movement or literary school (“l’École fumiste”) together with decadent and symbolist literary movements, reducing it to so-called mystification contests organized by the comedian named Sapeck and the writer Alphonse Allais, both designated as leaders of “l’École fumiste” around 1880. Yet, rather than viewing fumist productions as aimless provocations and assimilating Rimbaud’s work as an example of this “fumisterie” and decadence, this thesis examines the underlying presuppositions of language that are operative in the novel understanding of literature it entails. In this perspective, “fumism,” as a theory of discourse and literary practice, signals the emergence of a new vision of language and literary production. Against this background, this thesis presents a detailed historical reading of fumism in the context of literary debates in late nineteenth-century France. At the same time, this study shows how the reception of fumist works leads to a transformed economy of meaning and, above all, to a reconfiguration of literary understanding. As this study details, fumist productions (essentially poems and caricatures that can be viewed in the Album zutique, the main corpus) are based on rebuses. Remarkably exemplified by Rimbaud’s controversial sonnet “Voyelles”, this new meaning economy creates what are termed “documents”, which place the materiality of the text on a par with its potential meanings. In interpreting this transformation, the thesis concludes by demonstrating how this new understanding of meaning lays the groundwork for the artistic economy of the twentieth century – in particular, with regard to the dynamic mode of perception introduced by the father of the animated film, the fumist Emile Cohl.

This theoretical and empirical interdisciplinary thesis examines censorship in cinematographic import to Czechoslovakia during the 1960s and 70s. Specifically we focus on English-spoken movies dubbed into Czech. The thesis summarizes existing theoretical research on the present topic and complements it with data acquired through interviews with contemporary witnesses. This information is then used for an analysis of two movies released to cinemas in Czechoslovakia during the researched period - The Entertainer (in Czech Komik, 1960) and Twelve Angry Men (in Czech Dvanáct rozhněvaných mužů, 1957). The thesis ends with a comparison of these two dubbings in their respective context and of the 1960s and 1970s from the perspective of the Czechoslovak dubbing. Finally, it offers several topics for further research.

Six courts récits, qui peuvent n’en former qu’un, se penchent sur les possibilités de la voix narrative (à la troisième personne, au « je », au « nous », au « tu »). Ils réfléchissent sur l’acte de création comme construction et sur les effets de la narration. Pour preuve, le dernier texte reprend intégralement le premier. Le fantastique surgit au moment de l’hésitation du lecteur devant la nature des faits qui lui sont présentés. C’est avec les différentes instances que composent les destinateurs et les destinataires du récit que ce texte joue. La voix narrative, dans un texte fantastique, a une grande importance et doit créer une tension chez le lecteur, qui n’arrivera pas à trouver une explication pour certains aspects du récit. Le narrateur, souvent au « je », se confond avec un personnage. À l’aide de l’analyse du déroulement de l’intrigue et des procédés narratifs utilisés dans trois nouvelles : La Vénus d’Ille (Mérimée), Apparition (Maupassant), Ligeia (Poe), nous cherchons à montrer le rôle du narrateur dans le texte fantastique.
Six short stories, which can be grouped into one long story, provide different styles for the narrator: a third-person narrative, an ‘’I’’ narrative, a ‘’we’’ narrative, and a ‘’you’’ narrative. This particular text is a reflection about the act of creating as a progressive construction as well as a reflection on the effects of narration. As a concrete proof, the last part is identical to the first one, but having the whole story in mind gives the same text a different meaning. The fantastic mood emerges with the reader’s hesitation of how to interpret the facts that are presented to him. Globally, this text plays with the instances that provide a literary text and the ones that receive it. The narrative in a fantastic text is very important, and has to create tension in the reader, who will not be able to explain certain aspects of the story. Often, the plot is told in the first person, hence merging the narrator with a character, thus creating a double personality. We try to shine the light on the role of the narrator in a fantastic text by analyzing how the plot unravels and which narrative methods are used in three short stories: La Vénus d’Ille (Mérimée), Apparition (Maupassant), and Ligeia (Poe).

Ceramides are group of lipids which belong to sphingolipids. Skin ceramides have several functions in the organisms. They are important part of the lipid matrix of the stratum corneum, the outermost layer of the epidermis, where they participate in the barrier function of the skin. Furthermore, ceramides are secondary messengers in cell apoptosis and participate in many metabolic processes. Ceramides are composed of sphingoid base, which is N-acylated by fatty acid. Sphingoid base can be sphingosine, phytosphingosine, dihydrosphingosine or 6- hydroxysphingosine. Lower level of ceramides in the stratum corneum is associated with various skin diseases especially atopic dermatitis and psoriasis. Manifestations of these diseases is significantly improved by topical administration of ceramide. Exogenously administered ceramides help regenerate damaged skin and improve hydration of the skin. However, it is not fully known, in which way topically administered ceramides improve the progress of diseases. The aim of this work is synthesize physiological ceramide NS by using Grubbs metathesis reactions and optimize the conditions for achieving the highest yields. Synthesis of ceramide NS was based on pentadecan-1-ol, which was eliminated to terminal alkene. The elimination was carried out in three different...

Wydział Biologiczno-Chemiczny. Instytut Chemii.
Metateza olefin jest katalitycznym procesem wymiany wiązań podwójnych pomiędzy atomami węgla. W pracy przedstawiona została synteza oraz zbadany został profil aplikacyjny 7 nowych katalizatorów typu Hoveydy II. Pięć z nich zawierało w części benzylidenowej fragment 6-hydroksychromano- i 2H 3,4-chromenometylidenowy. Układy te wchodzą w skład struktury tokoferoli, w których występują specyficzne efekty stereoelektronowe warunkujące wysoką aktywność biologiczną witaminy E. Dwa pozostałe katalizatory zmodyfikowane zostały w obrębie N-heterocyklicznego karbenu, poprzez wprowadzenie w strukturę NHC fragmentu eteru koronowego. Łańcuch ten miałby stanowić osłonę steryczną aktywnego centrum katalizatora i wymuszać cis-orientację podstawników alkilowych przy tworzącym się na etapie przejściowym rutenacyklobutanie (powstawanie Z-izomeru). Nowe katalizatory zostały zbadane w reakcjach cyklizacji metatetycznej, metatezy krzyżowej i enyn. Uzyskane wydajności w wielu przypadkach były wyższe od tych osiąganych przy zastosowaniu katalizatorów handlowo dostępnych. Stosunek izomerów E/Z w utworzonych z użyciem nowych kompleksów alkenach był zbliżony do tych otrzymanych z wykorzystaniem znanych. Nowe katalizatory zostały z powodzeniem zastosowane w syntezie glikokoniugatu tokoferolu zawierającego pięciowęglowy nienasycony łańcuch, łączący α tokoferol z resztą cukrową. W pracy przedstawiona została również wydajna synteza katalizatora Hoveydy II generacji wychodząc z chlorku rutenu(III). Nie wymaga ona wyspecjalizowanej aparatury ani drogich, niebezpiecznych substratów.

Potrzeba było ponad pół wieku badań by metateza olefin z ciekawostki naukowej stała się jedną z podstawowych przemian katalitycznych stosowanych w syntezie organicznej. Dzięki wnikliwemu poznaniu reguł kierujących działaniem tej reakcji badacze mają możliwość zastosowania metatezy w coraz bardziej wymagających warunkach. Do takich należy m. in. wykorzystanie dienów w syntezie dużych pierścieni, które z uwagi na ich cenne właściwości zapachowe są szczególnie interesujące dla przemysłu perfumeryjnego. Aby uzyskać zadowalającą wydajność w tym procesie, należy prowadzić reakcję w bardzo wysokim rozcieńczeniu (typowo ok. 5 mM). Pozwala to uniknąć konkurencyjnej reakcji ADMET (ang. acyclic diene metathesis) prowadzącej do powstania polimerów. Inspirując się wcześniejszymi doniesieniami literaturowymi zdecydowałem się sprawdzić, czy możliwe jest wykorzystanie układu heterogenicznego składającego się z kompleksu rutenu umieszczonego w klatce MOF-a (ang. Metal-Organic Framework), aby w kontrolowany sposób ograniczyć dostęp substratu do katalizatora. Dzięki temu w danej chwili tylko jedna cząsteczka dienu miałaby możliwość kontaktu z kompleksem rutenu, co prowadziłoby wyłącznie do powstania produktu makrocyklizacji. W tym celu wykorzystałem komercyjnie dostępny katalizator FixCat, który osadziłem na MOFie (Al)MIL-101-NH3Cl. Jako substrat modelowy wybrałem dek-9-enian heks-5-en1-ylu, który ze względu na wyższą trudność w formowaniu docelowego pierścienia cieszy się mniejszą popularnością niż inne prekursory układów makrocyklicznych. Zanim przystąpiłem do badania zachowania układu w rosnącym stężeniu mieszaniny reakcyjnej, dokonałem krótkiej optymalizacji warunków reakcji, włączając w to badanie wpływu rozpuszczalnika i temperatury na przebieg reakcji. Przeprowadzone badania nie wykazały, aby układ FixCat@(Al)MIL-101-NH3Cl faworyzował powstawanie makrocyklicznego laktonu. Porównując aktywność badanego układu z analogicznym kompleksem homogenicznym zauważyłem, że zakotwiczony na nośniku katalizator FixCat pozwala na otrzymanie produktów z nadzwyczaj wysoką selektywnością. Innymi słowy nie obserwowałem produktów izomeryzacji wiązania podwójnego w mieszaninie reakcyjnej. Jest to dotychczas nieopisany wpływ nośnika na selektywność reakcji. Problem przemieszczania się wiązania podwójnego w trakcie reakcji jest bardzo dobrze znany w literaturze. W rezultacie powstają olefiny różniące się długością łańcucha alkilowego, które z uwagi na bardzo podobne właściwości fizykochemiczne względem głównego produktu stanowią trudny do usunięcia produkt uboczny. Aby w klarowny sposób wykazać skuteczność oraz użyteczność badanego przeze mnie układu sprawdziłem czy jego wysoka selektywność będzie widoczna również w reakcjach metatezy krzyżowej terminalnych olefin. Metateza krzyżowa może posłużyć jako metoda waloryzacji niższych olefin. Ścieżka ta pozwala w tani sposób otrzymać produkty szeroko stosowane jako plastyfikatory lub po odpowiednim przetworzeniu – detergenty. Ze względu na skalę produkcji kluczowe jest zminimalizowanie kosztów syntezy. W związku z tym poszukiwane są aktywne i trwałe katalizatory, które można użyć w śladowych ilościach (rzędu kilku części na milion), a praca w warunkach bezrozpuszczalnikowych nie prowadzi do ich przedwczesnego rozpadu. Co więcej, w wymaganiach stawianych przez przemysł często pojawia się warunek, aby otrzymany produkt był wolny od produktów izomeryzacji wiązania podwójnego. Badany przeze mnie układ katalityczny spełniał ostatni z wymienionych warunków. W dalszej części dysertacji zdecydowałem się sprawdzić pozostałe wymagania oraz porównać uzyskane wyniki z rezultatami otrzymanymi przy zastosowaniu komercyjnie dostępnych kompleksów, których nie osadzałem na nośnikach. Związkiem modelowym był 1-okten, którego budowa pozwalała na łatwe i jednoznaczne porównanie aktywności oraz selektywności przy użyciu prostych instrumentów analitycznych, takich jak chromatografia gazowa. W swojej pracy zbadałem również inne nośniki, takie jak UiO-76 czy NU-1000, a następnie wyznaczyłem zakres stosowalności układu FixCat@(Al)MIL-101-NH3Cl prowadząc reakcje olefin zawierających różne grupy funkcyjne. Dla wybranych przykładów sfunkcjonalizowanych olefin sprawdziłem w jakim stopniu produkty reakcji są zanieczyszczone produktami rozpadu katalizatora. Wraz z postępem reakcji rośnie stosunek produktu do substratu rośnie, co ze względu na równowagowy charakter tej przemiany, przekłada się na coraz większą ilość cykli nieproduktywnych w reakcji metatezy. Dlatego dalsze próby zwiększenia produktywności układu katalitycznego skłoniły mnie do zmiany podejścia w prowadzeniu reakcji metatezy krzyżowej. Wykorzystałem fakt, że używane przeze mnie substraty i otrzymywane z nich produkty różnią się temperaturą wrzenia i przeprowadziłem szereg reakcji wykorzystując ideę ekstrakcji ciągłej. W ten sposób raz utworzona cząsteczka substratu nie ma możliwości ponownego kontaktu z katalizatorem. Pozwoliło mi to uzy- skać bardzo wysokie wartości TON, jednakże selektywność w przypadku wyżej wrzących olefin nie była już tak korzystna, jak w reakcjach prowadzonych w klasyczny sposób. Podsumowując, badany przeze mnie układ katalityczny mimo pewnych mankamentów okazał się wartym uwagi w kontekście przetwórstwa olefin, zwłaszcza w warunkach wysokiej temperatury i wysokiego stężenia. Uzyskane wyniki posłużyły do przygotowania zgłoszenia patentowego oraz będą opublikowane.
It took more than half a century of research to turn olefin metathesis from a scientific curiosity into one of the basic catalytic changes used in organic synthesis. Thanks to a careful investigation of the rules that guide this reaction, researchers are able to apply metathesis in increasingly demanding conditions. These include the use of dienes in the synthesis of large rings, which due to their valuable fragrance properties are of great interest to the perfume industry. In order to obtain satisfactory performance in this process, the reaction should be carried out in very high dilution (typically about 5 mM). This avoids the competitive reaction of ADMET (acyclic diene metathesis) leading to polymers. Inspired by previous literature reports, I decided to investigate whether it is possible to use a heterogeneous system consisting of a ruthenium complex placed in a MOF (Metal-Organic Framework) to control the access of the substrate to the catalyst. This would allow only one dietary molecule to come into contact with the ruthenium complex at a given time, which would only lead to the creation of a macrocyclic product. For this purpose, I used a commercially available FixCat catalyst, which I deposited on the (Al)MIL-101-NH3Cl MOF. As a model substrate, I chose hex-5-en-1-yl dec-9-enoate, which, due to the higher difficulty in forming the target ring, is less popular than other precursors of macrocyclic compounds. Before I started to study the behaviour of the system in increasing concentration of the reaction mixture, I made a short optimisation of the reaction conditions, including the study of the effect of the solvent and temperature on the reaction course. The conducted tests did not show that the FixCat@(Al)MIL-101-NH3Cl system favoured the formation of macrocyclic lactone. Comparing the activity of the tested system with an analogous homogeneous complex, I noticed that the FixCat catalyst supported on the carrier allows to obtain products with extremely high selectivity. In other words, I did not observe products of double bond isomerisation in the reaction mixture. This is the unknown effect of the carrier on the selectivity of the reaction. The problem of the movement of the double bond during the reaction is very well known in literature. The result is the formation of olefins differing in length of the alkyl chain, which, due to very similar properties in relation to the main product, are a difficult to remove by-product. In order to clearly demonstrate the effectiveness and usefulness of the system I am investigating, I checked whether its high selectivity will also be visible in the cross-reaction of the terminal olefin metathesis. Cross-metathesis can serve as a method of valorising lower olefins. This pathway allows for obtaining products widely used as plasticisers or, after appropriate processing, detergents in a cheap way. Due to the scale of production it is crucial to minimise the costs of synthesis. Therefore, active and durable catalysts are wanted, which can be used in trace amounts (several parts per million), and working in solvent-free conditions does not lead to their early decomposition. What is more, the requirements of the industry often require that the resulting product be free of double bond isomerisation products. The catalytic system I was testing met the last of these conditions. In the further part of the dissertation I decided to check the remaining requirements and compare the results obtained with the ones achieved with the use of commercially available complexes, which I did not set on the carriers. The model compound was 1-octene, whose structure allowed for easy and unambiguous comparison of activity and selectivity using simple analytical instruments such as gas chromatography. In my work I also examined other carriers, such as UiO-76 or NU-1000, and then I determined the applicability range of the FixCat@(Al)MIL-101-NH3Cl system by conducting olefin metathesis reactions of alkenes containing different functional groups. For selected examples of functionalized olefins, I checked the extent to which the reaction products are contaminated with catalyst decomposition products. As the reaction progresses, the ratio of product to substrate increases, which, due to the equilibrium nature of this transformation, results in an increasing number of non-productive cycles in the metathesis reaction. Therefore, further attempts to increase the productivity of the catalytic system have led me to change my approach to conducting the cross-metathesis reaction. I have taken advantage of the fact that the substrates I use and the products I obtain from them differ in their boiling point and I have carried out a number of reactions using the idea of continuous extraction. In this way, once formed, the substrate molecule cannot come into contact with the catalyst again. This allowed me to obtain very high TON values, but the selectivity for higher-boiling olefins was no longer as favourable as in the classic approach. In conclusion, the catalytic system I studied, despite some disadvantages, proved to be worthwhile in the context of olefin processing, especially in high temperature and high concentration conditions. The results obtained were used to prepare the patent application and will be published

Cardanols are more and more used in the industry of polymers, resins, coatings, friction materials, etc. At right conditions, these lipid-like chemicals can undergo metathesis reaction. The main aim of the diploma thesis is an analysis of products of cardanol metathesis by HPLC-MS/MS. Standard 3,3'-hexadec-8-en-1,16-diyldiphenol, one of the main products of cardanol metathesis, was prepared for quantitative HPLC analysis. The standard was prepared in two steps. The first step was cardanol ethenolysis to give 3-(non-8-enyl)phenol. The second step was self-metathesis of 3-(non-8- enyl)phenol to give 3,3'-hexadec-8-en-1,16-diyldiphenol. The standard was characterised by HPLC/MS, MS/MS, EI-MS, UV/VIS, IR, Raman a NMR spectroscopy. The second part of the thesis is dedicated to the study of a mechanism of double-bond localization method in long chain hydrocarbons by acetonitrile APCI-MS. The formation of adducts [M + 55]+ , which are the key substances of this method, was studied using simple alkene models by MS and MS/MS. At the end, the structure and the mechanism of the formation of adducts [M + 55]+ were suggested. Key words: Cardanol, olefin metathesis, HPLC-MS, double-bond localization, APCI, acetonitrile

The purpose of this thesis is to analyze two Spanish versions of Čapek's drama R. U. R. with regard to the English text they both originate from. The theoretical part examines the phenomena of indirect translation, metatextuality (especially as far as adaptations for children are concerned) and translation of theatre plays according to Jiří Levý (1963). In the empirical part, R. U. R. is first analyzed with regard to various quotes the author himself said about his play. Next, Paul Selver's English version of R. U. R. is examined: it is explained how the text originated, what kind of changes it contains in comparison to the original text and how it was received. Finally, the thesis focuses on Consuelo Vázquez de Parga's Spanish rendition of R. U. R., which is a translation of Selver's English text. Again, changes on both compositional & ideological-esthetical level and stylistic level are analyzed. Here, Popovič's (1975, 1983) typology of stylistic shifts and changes in translation was used as the main methodological instrument. Last but not least, the thesis also addresses Juan Cervera Borrás's Spanish adaptation of R. U. R. for youth theatre. Key words: R. U. R., Čapek, Spain, indirect translation, metatextuality, adaptation, mediating text, adaptations for children, Selver, Vázquez de Parga,...

Le texte qui suit, malgré son libellé onomastique (le nom « John Cage »), son orientation disciplinaire (la « théorie littéraire ») et sa visée thématique (« la révision du commentaire critique »), se place d’emblée dans une posture d’écriture et de création. Il consiste à proposer comme point de départ l’identité de la forme textuelle et de sa dérivation métatextuelle, en d’autres mots : de la voix citée et analysée avec l’autre voix citante et analysante. Cette prémisse dérive elle-même d’une confrontation locale : les spécificités et les idiosyncrasies de la textualité mise en place par John Cage à partir des années quarante (partitions littéraires des recueils Silence et A Year from Monday, mésostiches de M et X, réécritures et « writing through » d’Empty Words…). En effet, l’examen par la théorie littéraire d’un corpus aussi disséminé et « néologique » que l’est celui de John Cage pousse son rédacteur à poser la question de sa propre écriture (« autoréflexivité ») et à rendre possible une réalisation artistique personnelle (« performativité »). C’est donc à travers la contingence d’une langue et d’une subjectivité au travail que la théorisation (textuelle) du texte cherche ici à s’élucider et à s’écrire. Le travail commence par installer les modalités à la fois circulaires et circulatoires de la théorie littéraire, une tension rhétorique et épistémologique qu’il identifie sous le nom d’« aporie autoréflexive » (le texte théorique est concerné par la question de lui-même). Il s’efforce ensuite d’analyser la nouveauté de l’œuvre littéraire cagienne, en empruntant un schéma dialectique et antagoniste : d’un côté, une « textualité-objet », originale et orthographique, de l’autre, une « textualité-sujet », disséminante et intertextuelle, anarchique et jubilatoire. Enfin, le texte propose la révision, la recomposition, la « réécriture » du commentaire critique sur les bases nouvelles d’une textologie autoréflexive et performative — une indiscipline d’écriture qui utilise sciemment les coordonnées linguistiques de son élocution (néologie, typographisme, procédés citationnels…) et qui fait place sans camouflage ou refoulement à la personnalité intertextuelle, contextuelle, métissée du rédacteur. Par l’entremise d’une sorte d’« exemplarité textuelle » (Cage), ce travail insiste pour une synthèse à la fois productive et expressive des voix analysées et analysantes dans les études littéraires. On verra que, par moments, cette proposition implique que le texte se marginalise.
The following text, despite its onomastic labelling (the name “John Cage”), its disciplinary orientation (“literary theory”), and its thematic aim (“the revision of the literary commentary”), positions itself as a writing and creative venture. It starts by stating the strict identity of texts and metatexts, in other words, of the quoted, analyzed voice, with the quoting, analyzing other voice. This premise derives from a specific confrontation: the specificities and idiosyncrasies of John Cage’s literary production since the late 1940s (the literary scores from the anthologies Silence and A Year from Monday, the mesostics from M and X, the rewritings and “Writing through’s” from Empty Words…). Indeed, the examination by literary theory of a body of work as disseminated and “neological” as John Cage’s encourages the literary critic or theoretician to ask the question of his own writing (“self-reflexivity”) and also to make possible an original artistic realization (“performativity”). It is therefore through the possibilities of a language and of a subjectivity at work that the (textual) theorization of texts tries herein to elucidate and to write itself. This work starts by setting up the modalities both circular and circulatory of literary theory—a rhetorical and epistemological tension that will be identified as the “self-reflexive aporia” (the theoretical text is primarily concerned by the question of itself). It then tries to analyze the novelty of Cage’s literary work, using a dialectical and antagonistic configuration: on one hand, an “objective textuality”, original and orthographical; on the other hand, a “subjective textuality”, disseminating and intertextual, anarchic and unrestrained. Finally, this text proposes the revision, recomposition and “rewriting” of the critical commentary on the basis of a new self-reflexive and performative textology. That is: a sort of undiscipline in writing that knowingly manoeuvres the linguistic coordinates of its elocution (neology, typographism, quotation processes…) and that does not try to conceal or repress the intertextual, contextual, heterogenous and disparate personality of its author. Through a sort of “textual exemplarity” (Cage), this work insists on a synthesis both productive and expressive between the voices analyzing and the voices being analyzed. We will see accordingly that this proposition implies, from time to time, that the text be marginalized.
Toutes les illustrations qui ponctuent cette thèse ont été réalisées par Chantal Poirier. Elles ont été insérées dans le texte selon un ordre méticuleusement aléatoire.

The main emphasis of the dissertation focuses on the preparation of new heterogeneous metathesis catalysts, their characterization, and testing their activity and selectivity in different metathesis reactions. This work has been completed at the Department of Synthesis and Catalysis, J. Heyrovský Institute of Physical Chemistry, AS CR. Hoveyda-Grubbs type catalyst ZC (Zhan catalyst 1-B) was immobilized on mesoporous molecular sieves of different architecture and pore diameter, d, (hexagonal: MCM-41, d = 4.0 nm; SBA-15, d = 6.8 nm; SBA-15 large pore (LP), d = 11.1 nm and cubic: MCM-48, d = 6.0 nm) and conventional silica (Merck) for comparison. The immobilization was done by simple mixing of ZC solution with appropriate support at room temperature. Ru loading in all immobilized catalyst was 0.93 wt%. The catalysts and supports were characterized by X-ray diffraction and nitrogen adsorption measurement. XPS and UV-Vis spectroscopic studies of ZC immobilized on SBA-15 (ZC/SBA-15) indicated the attachment of ZC on mesoporous sieve surface by non-covalent interactions. The immobilized catalysts exhibited high activity and 100% selectivity in ring-closing metathesis of diethyl diallylmalonate and 1,7-octadiene, in metathesis of methyl oleate and methyl 10-undecenoate, and in the ring-opening metathesis...

Paliwa kopalne, takie jak ropa naftowa, gaz ziemny czy węgiel ulegną w przyszłości wyczerpaniu, a skutki tego braku odczują zarówno sektory energetyczny czy petrochemiczny, jak również inne branże, dla których np. ropa naftowa jest kluczowym surowcem w produkcji materiałów. Zastosowanie surowców odnawialnych w kontekście zamiennika dla paliw kopalnych jest atrakcyjną i wręcz nieuniknioną alternatywą. Do ciekawych i wartościowych przemian należą transformacje pochodnych wyższych nienasyconych kwasów tłuszczowych np.: estrów, nitryli lub alkoholi. Coraz częściej jako narzędzia do ich przekształceń używa się reakcji metatezy olefin. Do niezwykle ważnych przykładów można zaliczyć reakcje alkenolizy pochodnych estrowych, zarówno w skali laboratoryjnej jak i przemysłowej. Nienasycone kwasy tłuszczowe z jednym (kwas oleinowy) lub kilkoma (kwas linoleinowy) wiązaniami podwójnymi są prekursorami wartościowych związków jak kwas 9-dekenowy oraz 1-deken. Celem badań prowadzonych w ramach mojej pracy doktorskiej były transformacje pochodnych estrowych kwasu oleinowego i 9-dekenowego. Jako pierwsze zbadałem reakcje oleinianu etylu w obecności 2-metylo-2-butenu. W trakcie eksperymentów uwagę skupiłem na zastosowaniu i przebadaniu dostępnych handlowo kompleksów. Zoptymalizowałem warunki prowadzenia reakcji, a przeprowadzone w dalszej kolejności testy reaktywności pozwoliły na wybór aktywnych i selektywnych kompleksów mogących znaleźć szersze zastosowanie w wariancie przemysłowym. Chociaż nie udało mi się określić jednoznacznych zależności pomiędzy strukturą kompleksów, a ich skutecznością w reakcji metatezy krzyżowej, zauważyłem pewne trendy. Po pierwsze stwierdziłem, że reakcja metatezy krzyżowej może być skutecznie prowadzona przy użyciu katalizatorów rutenowych drugiej generacji. Stwierdziłem również, że katalizatory Hoveydy-Grubbsa są bardziej aktywne, w porównaniu z kompleksami typu indenylidenowego i Grubbsa. W drugiej części zbadałem możliwość użycia pochodnych estrowych kwasu oleinowego i 9-dekenowego w syntezie makrocyklicznych laktonów. W procesie optymalizacji znalazłem dogodne warunki prowadzenia reakcji umożliwiające efektywną syntezę związków makrocyklicznych. Po raz pierwszy w toku moich badań pojawił się i wyraźnie zaznaczył wpływ podstawników alkilowych obecnych przy wiązaniach podwójnych wyraźnie rzutując na wydajność cyklizacji w roztworze. Rezultaty jasno pokazały, że dieny posiadające dwa terminalne wiązania podwójne cyklizują z niższymi wydajnościami niż ich analogi zawierające podstawione wiązanie nienasycone. W trakcie tego etapu badań udało mi się w pewnym stopniu określić optymalną strukturę substratu. Konieczność używania dużych objętości niepolarnych rozpuszczalników skłoniła mnie do szukania alternatywy dla standardowych mediów reakcyjnych jak chlorek metylenu czy toluen. Przeprowadziłem serię testów z użyciem octanu etylu jako rozpuszczalnika uzyskując dobre rezultaty w szerokim zakresie stężeń (1,5-100 mM). Poszukiwania granicznego stężenia, w którym reakcja makrocyklizacji zachodziłaby w dalszym ciągu wydajnie i efektywnie skłoniły mnie do prowadzenia reakcji w warunkach obniżonego ciśnienia, w zakresie 10-3-10-6 mbar. Opracowałem efektywną procedurę otrzymywania makrocyklicznych laktonów z dobrymi wydajnościami w stężeniu 0,2 M z użyciem dyfuzyjnej pompy olejowej. Mając na uwadze aplikacyjne zastosowanie procesu postanowiłem przeprowadzić reakcję przy użyciu bardziej dostępnych rotacyjnych pomp olejowych (próżnia rzędu 10-3 mbar). Przeprowadzone badania pokazały, że kluczowy dla procesu jest czas prowadzenia reakcji. W końcowym etapie badać zwiększyłem stężenie dienu w mieszaninie reakcyjnej z 0,2 M do 0,7 M (odpowiednio 9 %wag. oraz 33 %wag.). Z pewnym sukcesem udało mi się również przeprowadzić reakcje w stężeniach 1,4 oraz 1,9 M (odpowiednio 67 %wag. oraz 90% wag.).
It is well known that fossil fuels such as oil, natural gas or coal will be depleted in the future, and the effects of this shortage will be felt by both energy and petrochemical sectors, as well as other industries for which, for example, crude oil is a key raw material in production of different materials. The use of renewable raw materials in the context of a substitute for fossil fuels is an attractive and almost unavoidable alternative. The transformations of higher unsaturated fatty acids derivatives mainly: esters, nitriles or alcohols, the most interesting and valuable transformations. Increasingly, olefin metathesis is used as a tool for their transformation. Unsaturated fatty acids with one (oleic acid) or several (linoleic acid) unsaturated bonds are precursors of valuable compounds such as 9-decenoic acid and 1-decene. The aim of my research were transformations of the esters derivatives of oleic acid and 9 decene. First, I tested the reaction of ethyl oleate in the presence of 2-methyl-2-butene. During the experiments, my attention was focused mostly on commercially available metathesis complexes. Using commercially available catalysts, I optimized reaction conditions, which would allow to obtain a high substrate conversion while maintaining the optimal level of selectivity of the products. Subsequent tests of reactivity allowed for the selection of active and selective complexes. Although I did not manage to determine clear relationships between the structure of complexes and their effectiveness in the cross-reaction of the metathesis, I noticed some trends. First of all, I found that the metathesis reaction can be effectively carried out using second generation ruthenium catalysts. Compared with indenylidene and Grubbs type complexes, I found that the Hoveyda-Grubbs catalysts are more active. In the second part of the research I investigated ester derivatives of oleic acid and 9-decenoic acid as precursors in the synthesis of macrocyclic lactones. In the optimization process, I found conditions for conducting reactions that enable effective synthesis of macrocyclic compounds. I observed the effect of alkyl substituents present on double bonds, clearly affecting the efficiency of cyclization in the solution. The results showed that dienes having two terminal double bonds cyclize with lower yields than equivalents containing a substituted unsaturated bond. During this stage of the research, I managed to some extent to determine the optimal structure of the substrate. Further experiments showed that in order to improve the macrocyclization efficiency and, at the same time, reduce the amount of by-products resulting from oligomerization, it effectively prevents the presence of methyl substituents at double bonds. The economic barrier to the macrocyclization reaction is the need for high dilutions. It prompted me to look for an alternative to standard solvents like methylene chloride or toluene. I conducted a series of tests using ethyl acetate as a solvent, obtaining good results in a wide range of concentrations. The search for a limit concentration in which the macrocyclization reaction would continue to be efficient and effective prompted me to conduct a reaction using a vacuum in the range of 10-3 - 10-6 mbar. I managed to show that it is possible to obtain macrocyclic lactones with good yields at 0.2 M using a diffusion oil pump. Bearing in mind the application of distillation of combined macrocyclization, I decided to carry out an identical process of macrocyclization combined with distillation using much more available rotary oil pumps (vacuum of 10-3 mbar). The conducted research has shown that the reaction time is crucial for the process. With some success, I was able to carry out reactions at a concentration of 67 wt% and 90 wt% (1.4 and 1.9 M., respectively).

Metateza alkenów jaki i alkinów jest wysoce użytecznym narzędziem syntetycznym, ponieważ otrzymywane są w niej związki zawierające wiązania wielokrotne, które mogą być poddane kolejnym transformacjom prowadzącym do złożonych cząsteczek niejednokrotnie trudnych do uzyskania innymi metodami. Jednak zakres stosowalności metatezy krzyżowej jest ograniczony przez brak skutecznych metod kontroli selektywności tej reakcji. Dlatego opracowanie metod selektywnego prowadzenia metatezy krzyżowej stanowiło główny cel niniejszej rozprawy. Etapy pracy obejmowały: a) syntezę substratów do łączenia - pochodnych propynylobenzenu, b) łączenie substratów z łącznikiem przez grupy funkcyjne – w wyniku którego uzyskałam pochodne meta i para, c) łączenie substratów z łącznikiem poprzez utworzenie wiązania Si-C – w wyniku którego uzyskałam pochodne orto, d) testowanie związków w metatezie alkinów, e) obliczenia kwantowo-chemiczne, f) syntezę pochodnych disiloksanowych i testowanie ich w metatezie alkenów. Przeprowadzone badania, doprowadziły do opracowania przeze mnie struktur trzech różnych łączników, które zastosowałam w syntezie ośmiu różnych związków. Jeden z zaproponowanych łączników okazał się być użytecznym narzędziem w syntezie kombretastatyny A4. Możliwe są modyfikacje łącznika, które pozwolą na dostosowanie jego budowy do struktury innych substratów, które mają być poddane makrocyklizacji. Prowadząc reakcję metatezy zaobserwowałam, że miejsce przyłączenia łącznika w pierścieniu cząsteczki ma wpływ na jej reaktywność. W żadnym z zaproponowanych przypadków nie dochodziło do degradacji łącznika na etapie metatezy, co świadczy o właściwym doborze łączników do warunków reakcji. Sukcesem zakończyła się próba usunięcia po przeprowadzeniu reakcji metatezy jednego z łączników z cząsteczki. Okazało się, że zaproponowane połączenie jest na tyle labilne, że na etapie modyfikacji postmetatetycznych (podczas reakcji uwadarniania) ulega samorzutnemu usunięciu z cząsteczki. Badania teoretyczne doprowadziły do uzyskania informacji o strukturze przestrzennej i energii wybranych związków - zawierających i nie zawierających łączników silanowych. Pozwoliły również na ustalenie optymalnej długości łańcucha dla związków łączonych w różnych pozycjach. Zaproponowany łącznik można z powodzeniem stosować do łączenia substratów zarówno poprzez wiązania krzem-tlen jak i krzem-węgiel, a wnioski płynące z obliczeń teoretycznych stosować do optymalizacji jego długości w zależności od struktury stosowanych substratów.
Both olefin and alkyne metathesis reactions constitute as very useful synthetic tools for the synthesis of compounds containing multiple bonds, which can be further transformed to highly complex molecules, that are often difficult to obtain by other methods. However, their applicability is limited by the lack of effective methods to control the selectivity of cross-metathesis reactions. Therefore, the development of selective cross-metathesis has constituted to be the main goal of this research, and included: a) the synthesis of substrates for linking – propynylbenzene derivatives b) linking substrates with linkers through functional groups, which has led to forming meta and para derivatives c) linking substrates with linkers by the formation of the carbon-silicon bond, resulting in forming orto derivatives d) testing compounds in alkyne metathesis reaction, e) quantum chemical calculations, f) synthesis of disiloxane derivatives and the investigation of their applicability within olefin metathesis. The conducted studies have led to the development of three different linkers, subsequently used in the synthesis of eight different compounds. One of the proposed linkers can be useful in the synthesis of Combretastatine A4. It is also possible to tailor the structure of linkers, so they can be adapted to the structure of substrates which shall be macrocyclized. Investigation of the metathesis reaction has revealed that the position of the linker in the molecule ring affects its reactivity. All linkers have been stable under the reaction condition, which confirms the proper choice of the latter with regard to the reaction conditions. Additionally, one of the linkers has been also successfully removed from the molecule after the metathesis reaction. This shows that the proposed linker is labile enough for the spontaneous removal from the molecule at the postmetathetical stage. Theoretical studies have allowed for a deeper insight into the structure and energy of selected compounds, with and without silane linkers. They have also allowed to determine the optimal chain length for compounds linked at different positions. The proposed linker can be successfully used for connecting substrates both by silicon-oxygen and silicon-carbon bonds. Moreover, the conclusions driven from theoretical calculations can be used to optimize the length of linker, depending on the structure of the used substrates.

Praca poświęcona jest projektowaniu i syntezie nowych niesymetrycznych Nheterocyklicznych karbenów (NHC) i ich zastosowaniu jako ligandów w rutenowych (pre)katalizatorach reakcji metatezy olefin. Otrzymane kompleksy były przedmiotem badań dotyczących ich aktywności katalitycznej i stabilności. Wybrane (pre)katalizatory wykorzystano w reakcjach otrzymywania złożonych molekuł takich jak pochodne estronu i pregnenolonu, a także w diastereoselektywnym przegrupowaniu pierścienia. Wyniki badań wykazały, że charakter liganda NHC w sposób istotny wpływa na właściwości otrzymanych kompleksów rutenu a w konsekwencji na wyniki transformacji przeprowadzonych z ich udziałem.

Metateza olefin jest jedną z ważniejszych metod w nowoczesnej syntezie organicznej. Pomimo, że znana jest od płowy lat pięćdziesiątych, to dopiero w ciągu ostatnich kilkunastu lat stała się ważnym narzędziem w syntezie organicznej i w chemii polimerów. Największy rozwój metatezy nastąpił w 2005 r. kiedy Y. Chauvin, R. R. Schrock, R. H. Grubbs zostali uhonorowani Nagrodą Nobla za wkład w rozwój tej dziedziny. Głównym ograniczeniem stosowania metatezy jest brak uniwersalności. Oznacza to, że dany katalizator umożliwia efektywne przeprowadzenie reakcji tylko określonych klas substratów. Z tego powodu w laboratoriach na całym świecie trwają poszukiwania nowych katalizatorów metatezy olefin. Celem jest otrzymanie inicjatorów charakteryzujących się szerokim zakresem zastosowań. Modyfikacje struktury karbenowych kompleksów rutenu mogą dotyczyć fragmentu benzylidenowego, liganda N-heterocyklicznego, oraz ligandów anionowych. Celem moich badań była synteza serii kompleksów rutenowych, które w sferze koordynacyjnej posiadają zmodyfikowany ligand anionowy. Ponadto, aktywność otrzymanych związków badałam w szeregu modelowych reakcji metatezy oraz w reakcji polimeryzacji metatetycznej. Otrzymałam trzy klasy związków ze zmodyfikowanymi ligandami anionowymi: kompleksy posiadające ligandy jodkowe, amidkowe i fenolanowe. Dysertacja podzielona jest na trzy części. W pierwszej przedstawiłam dotychczasowy stan wiedzy o kompleksach posiadających modyfikacje anionowe. W drugiej części podzielonej na cztery podrozdziały przedstawiłam badania, które przeprowadziłam. W ostatniej opisałam procedury syntezy przeprowadzonych reakcji oraz analizy otrzymanych przeze mnie związków. Rozpoczynając pracę w zespole prof. Greli otrzymałam szereg kompleksów o modyfikacjach anionowych. Zainspirowałam się wcześniejszymi badaniami Slugovca, który otrzymał dijodkowe analogi katalizatora Hov-Gru-II i zbadał ich zastosowanie w reakcjach polimeryzacji. Do syntezy nowych kompleksów wybrałam jako prekursory kompleksy różniące się ligandami benzylidenowymi i obojętnym ligandem (np. katalizator CAAC – Bertranda). Nowe kompleksy badałam w reakcjach metatezy oraz porównałam ich aktywność z dichlorkowymi analogami. Kompleksy jodkowe okazały się bardzo dobrymi inicjatorami reakcji etenolizy, gdyż zastosowanie ich pozwoliło uzyskać produkty z bardzo wysoką selektywnością. W kolejnym etapie badań otrzymałam klasę katalizatorów III generacji posiadających N-chelatujący ligand amidkowy. Kompleksy te posiadały zmodyfikowany ligand N-heterocykliczny, beznylidenowy oraz różniły się ligandem pirydynowym. Związki te, są nieaktywne w reakcjach metatezy, natomiast dodatek in situ np. HCl lub TMSCl powodował gwałtowny wzrost aktywności. Ta chemiczna aktywacja została wykorzystana w modelowych reakcjach metatezy i reakcjach polimeryzacji. Sprawdziłam aktywność tych kompleksów również w reakcjach z bardzo niską ich ilością: stosując 500 ppm uzyskałam konwersję 80% i TON równy 1008, natomiast stosując 50 ppm otrzymałam 20% konwersji i TON 159. Katalizatory amidkowe również sprawdziłam w polimeryzacji dwóch monomerów: estru dimetylowego endo,egzo-bicyklo[2.2.1]hept-5-eno-2,3-dikarboksylowego i dicyklopentadienu. Użycie katalizatorów amidkowych umożliwia otrzymanie produktów polimeryzacji, które posiadają właściwości zbliżone do tych otrzymanych przy użyciu handlowo dostępnych inicjatorów. Właściwości otrzymanych polimerów badałam stosując analizy STA i DSC. Ostatnią grupą związków, którą otrzymałam były kompleksy posiadające O-chelatujący ligand fenolanowy. Ligandy O-chelatujące zostały wcześniej opisane przez Fogg i Verpoorta, ale w przypadku ich kompleksów ligand ten nie jest związany z fragmentem benzylidenowym. Kompleksy fenolanowe otrzymałam w reakcji handlowo dostępnych katalizatorów z 2-propenylofenolem. Zauważyłam również, że dodatek 3 równoważników tricykloheksylofosfiny powoduje wzrost wydajności. Wykazałam, że kompleksy te można aktywować chemicznie za pomocą kwasów, ponadto ich aktywność rosła po dodaniu perchloroalkanów (CCl4 i C2Cl6). Ponadto katalizatory te są bardzo stabilne i rozpuszczają się w szerokim spektrum rozpuszczalników: polarnych i niepolarnych. Właściwość ta, została wykorzystana w reakcjach polimeryzacji. Do badania polimeryzacji użyłam dwóch monomerów: estru dimetylowego endo,egzo-bicyklo[2.2.1]hept-5-eno-2,3-dikarboksylowego i dicyklopentadienu. Produkty polimeryzacji scharakteryzowałam za pomocą analizy DSC i STA. Ostatnim zagadnieniem, które zbadałam była aktywacja kompleksów fenolanowych za pomocą heksachloroetanu. Pierwszym eksperymentem było monitorowanie przebiegu reakcji pomiędzy kompleksem fenolanowych a C2Cl6 za pomocą spektroskopii NMR. W czasie pomiarów w probówce NMR wytrącił się osad, który okazał się być kompleksem rutenu na +3 stopnia utlenienia. Kolejne eksperymenty wykazały, że można przypuszczać iż pierwszym etapem aktywacji jest dysocjacja tricykloheksylofosfiny. Dzieje się to w obecności C2Cl6, z którym PCy3 tworzy najprawdopodobniej sól fosfoniową. Nowy kompleks rutenu na +3 stopniu utlenienia sprawdziłam z modelowej reakcji metatezy RCM - również okazał się być aktywowany chemicznie. Aby wyjaśnić to, przeprowadziłam eksperymenty w spektroskopii w podczerwieni i udowodniłam, że dodatek HCl powoduje tworzenie się wolnej grupy –OH.
Olefin metathesis is one of the most important method in modern organic synthesis. It was discovered in the mid-fifties of the last century, but only in the last few years has become an important tool in organic synthesis and polymer chemistry. The main limitation of the use of catalysts is a lack of versatility in practical application, ie. a particular catalyst efficiently catalyzes reactions only certain classes of substrates. Therefore, in many laboratories around the world the investigations on novel modification of catalysts are continued. The purpose of these research is to obtain a new catalysts characterized by a wide range of applications. These modifications may refers to both to the benzylidene ligand, N-heterocyclic ligand, or anionic ligands. In the literature the least explored is an anionic part of catalysts therefore I undertook to modified these ligands. The aim of the research was the synthesis of a series of new complexes routine, which have in the coordination sphere of the modified anionic ligand. In addition, I find out how these changes in the structure of (pre)catalyst will affect its activity with particular emphasis on their application to their performance in metathesis polymerization reactions. The study was started from the synthesis of complexes with iodide ligands instead of chloride ligands. In following experiments I obtained O- and N-chelating complexes which exhibit chemo-switchable properties. Moreover, one of the chapters was dedicated to the study of the mechanism of activation by chloroalkenes. The thesis is divided into three parts. In the first I present the current state of knowledge of complexes with modified anionic ligands. Another, was titled "Research" has four chapters, which describe experiments performed by me. In the final, Part III was described the procedure for reaction and analysis of the obtaining compounds. Beginning a PhD study under the supervision of prof. Grela, I decided to synthesis the series of complexes having modified anionic ligand. I inspired by the work of Slugovc whose described iodide analogues complex of Hov-Gru-II and their application in polymerization. These complexes exihibit interesting properties and activity so I decided to find out how similar catalysts will work in different type of metathesis. In my research I decided do apply a number of commercially available catalysts, typical complexes such as Hov-Gru-II type with modified benzylidene, and Bertrand catalyst containing CAAC ligand. I change chloride ligands to iodide ligands in these complexes. The aim was investigating the influence of that change. The new iodide catalysts were examined in model metathesis reaction and in ethenolysis of ethyl oleate. Synthetic pathway of these complexes is very simple and let to receive products with satisfactory yield. Activity iodide complexes was checked in RCM, CM, en-yn and self-CM and compare with activity of their chloride analogues. Iodide catalysts exhibit moderate activity in every reaction. Moreover I carried out ethenolysis. In this reaction was observed two relationships: presence of iodide ligands cause decreasing of reaction yield and increasing of selectivity. Further stage of my research was the synthesis of 3rd generation complexes containing N-chelating benzylidene lignad with amido group. During this project, I obtained a series of amido-complexes with different NHC, benzylidene and pyridine ligands. These compounds was obtained in simply one step reaction with high. Having a series of amido complexes I tested them in model metathesis reaction. I found, that complexes are inactive, but could be activated by addition of e.g. Lewis acids, HCl or chloroalkanes. Addition of additives cause dramatic increase of reactivity. I also checked them in low loading reaction. Using 500 ppm of initiator let to achieve conversion about 80% and TON equal 1008, and applying 50 ppm give 20% conversion and TON 159. Active forms of amido complexes are excellent initiators of metathesis reaction, both in the case of not complicated and challenging substrates. In these project, I mainly focus on activity amido catalysts in polymerization. I examined them in reaction with two monomers: endo,egzo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic dimethyl ester and dicyclopentadiene. I tested the influence of the solvent and temperature of reaction on resulting polymer. Properties of the products were checked in STA and DSC analysis. Properties of the polymers which I have received are comparable to polymers obtaining with commercially available catalysts. In the next research phase, I elaborated synthesis of ruthenium complexes with O-chelating phenolate type ligand. Complexes with phenolate ligand were described by Fogg or Verpoort but that ligands are not bonded with benzylidene fragment. In my project, I used commercially available catalysts as a ruthenium source and derivative of 2-propenylphenol and synthesized a family of 2nd and next 1st and 3rd generation catalysts. Following, I tested them in model metathesis reaction particular in polymerization. At the time of conducting the synthesis, I noticed that addition of 3 equivalents of tricyclohexylphosphine significantly increase the yield. Phenolate complexes have proven to be chemo-switchable, similar to amido catalyst. Besides, these catalysts are characterized by a high stability in solid and are soluble in wide range of solvent: polar and non polar. Using their unique properties, I got involved them in polymerization in neat. I also tested them in reaction with two monomers: endo,egzo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic dimethyl ester and dicyclopentadiene. Products of polymerization are characterized by satisfying properties in many tests (STA, DSC, TS). The last issue, I focused on activation phenolate complexes by chloroalkanes. During the study of phenolate complexes, I found that they are not reactive in metathesis reaction but after addition of for exaple HCl, TMSCl or chloroalkane reactivity significantly increase. As far as activation by HCl and TMSCl were known, addition of chloroalkanes has not been described. The investigation I started from the monitoring the progress of the reaction between phenolate complex and C2Cl2 by NMR spectroscopy. I got accidentally precipitation, which turned out to be ruthenium complex on +3 oxidation state. The structure was confirmed by rtg measurement. Due to successive experiments can be assumed that the first step of activation phenolate complex is dissociation of tricyclohexylphosphine. This is because of the presence of C2Cl6, which probably forming phosphate salt. The mechanism is presumably analogous to Apple reaction. Further research are under investigation in Grela`s group. In order to examine the properties of complex on +3 oxidation state a series of tests were performed. Besides, I checked that complex in model RCM reaction and was inactive but addition of HCl activated them. As a results, I used IR spectroscopy to explain that. I found that addition of HCl lead to forming active form of complex with free –OH group.

Metateza olefin stanowi jedną z najważniejszych metod tworzenia podwójnych wiązań węgiel-węgiel. Pierwsze heterogeniczne katalizatory metatezy olefin oparte były na kobalcie, molibdenie i wolframie jednak posiadały wiele wad m.in. wymagały stosowania wysokich temperatur oraz nie były kompatybilne z szeregiem grup funkcyjnych. Z tego względu opracowano dobrze zdefiniowane strukturalnie homogeniczne katalizatory rutenowe charakteryzujące się zwiększoną trwałością oraz możliwością przeprowadzenia reakcji metatezy olefin w niższych temperaturach. Znanych jest szereg katalizatorów rutenowych, jednak relacja łącząca strukturę z aktywnością nadal stanowi intensywne pole badawcze. Z tego względu próbuje się poznać tą zależność, która umożliwi projektowanie i otrzymywanie katalizatorów o założonej aktywności jak również pozwoli wyjaśnić obserwowane zmiany aktywności związane z wprowadzanymi podstawnikami. Celem pracy doktorskiej było zaprojektowanie, otrzymanie i zbadanie wpływu niesymetrycznie podstawionego układami tiofenu, furanu, benzotiofenu i benzofuranu liganda imidazolidyn-2-ylidenowego w katalizatorach rutenowych. W tym celu zaprojektowałem i otrzymałem 7 katalizatorów typu indenylidenowego i 2 katalizatory typu Hoveydy-Grubbsa. Zbadałem ich aktywność katalityczną w najważniejszych typach reakcji metatezy olefin: RCM (metateza zamknięcia pierścienia), RCEYM (metateza zamknięcia pierścienia alkeninów), CM (metateza krzyżowa), dRRM (metateza obejmująca diastereoselektywne przegrupowanie pierścienia). Zbadany został wpływ temperatury, możliwość przeprowadzenia reakcji w nieosuszonych i nieodtlenionych rozpuszczalnikach takich jak toluen i 2-metylotetrahydrofuran, będący ekologicznym rozpuszczalnikiem. W dalszej części pracy zaprojektowałem i zsyntetyzowałem 3 katalizatory typu Hoveydy-Grubbsa zawierające symetrycznie podstawiony N-heterocykliczny karben. Skupiłem się na modyfikacji liganda chelatującego, silnie elektronoakceptorowymi grupami arylosulfonianowymi w pozycji para do grupy izopropoksylowej. Otrzymane kompleksy wykazywały wysoką aktywność katalityczną w reakcjach testowych przeprowadzanych w chlorku metylenu, toluenie oraz w 2-metylotetrahydrofuranie. Wykonane badania poszerzają dotychczasową wiedzę dotyczącą zależności struktury katalizatora od reaktywności. Wyniki pracy zostały częściowo opublikowane w czasopiśmie Catalysis Communications[1], oraz są przedmiotem polskiego zgłoszenia patentowego[2]. [1] Smoleń, M.; Kędziorek, M.; Grela, K. “2-Methyltetrahydrofuran: Sustainable Solvent for Ruthenium-Catalyzed Olefin Metathesis” Catal. Commun. 2014, 44, 80-84. [2] Smoleń, M.; Grela, K. „Kompleksy rutenu, sposób ich wytwarzania oraz ich zastosowanie” Zgłoszenie patentowe w dniu 02.12.2014. Numer: P. 410 329.